Inorg. Chem.

1987, 26, 2467-2476 2467

Contribution from the Laboratoire de Synthese et d’Electrosynthese Organométallique associé au CNRS (UA 33),
Faculté des Sciences “Gabriel”, 21100 Dijon, France, Laboratoire de Minéralogie et Cristallographie associé au CNRS (UA 809),
Faculte des Sciences, Centre de 2eme Cycle, 54506 Vandoeuvre les Nancy, France,
and Department of Chemistry, University of Houston, Houston, Texas 77004

Metalioporphyrins with Metal-Metal Bonds. Synthesis and Characterization of

(P)InMn(CO)5, (P)InCo(CO)4, and (P)InM(CO)3Cp Where M = Cr, Mo, and W.
Molecular Stereochemistry of
[(2,3,7,8,12,13,17,18-Octaethylporphyrinato) indium (III) ]pentacarbonylmanganese
R. Guilard,*13 P. Mitaine,la,c C. Moise,la C. Lecomte,lb A. Boukhris,lb C. Swistak,10 A. Tabard,la,c
D. Lacombe,10 J.-L. Cornillon,10 and K. M. Kadish*10
Received December 11, 1986
The synthesis and physicochemical characterization of 10 metal-metal- -bonded indium porphyrins were investigated in nonaqueous
media. The ligands -bonded to indium tetraphenylporphyrin ((TPP)In) or indium octaethylporphyrin ((OEP)In) were Mn(CO)5,
Co(CO)4, W(CO)3Cp, Mo(CO)3Cp, and Cr(CO)3Cp. Each neutral complex was characterized by *H NMR, IR, and UV-visible
spectroscopy. On the basis of these data, the presence of a single metal-metal covalent bond was suggested, and this was confirmed
by a room-temperature single-crystal X-ray diffraction study. (OEP)InMn(CO)5 crystallizes in the triclinic system, space group
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Pi. Its lattice constants are as follows: a = 12.415 (3) A, b = 13.485 (2) A, c = 15.083 (3) A, a = 61.99 (2)°, 0 = 69.69 (2)°,
and 7 = 69.75 (2)° with Z = 2 (Z)„ptl = 1.44 g-cm"3), R(F) = 0.041, and RW(F) = 0.048 for 7346 unique reflections. The In-Mri
bond length is 2.705 (1) A, and the indium atom lies 0.744 (1) A from the plane of the four porphyrin nitrogens. The average
Mn-CO equatorial distance (1.839 (4) A) is longer than the axial one (1.809 (6) A). The electrochemistry of each -bonded
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complex was carried out in methylene chloride containing 0.1 M (TBA)PF6. Each metalloporphyrin could be electrooxidized,
but the bimetallic complex underwent a rapid cleavage of the metal-metal bond after the first one-electron abstraction. The
complexes could also be reversibly reduced by one or two electrons, but a cleavage of the metal-metal bond invariably occurred,
leading to formation of (P)In* and [ML]" entities. Some of the reduced compounds were stable for short times that depended
upon the specific axial ligand. In these cases a characterization of the reduced species was carried out. Finally, comparisons were
made between the reactivities and physicochemical properties of the investigated complexes and other alkyl or aryl -bonded indium
porphyrins that have been described in the literature.

Introduction lished. The former compound has also been examined by IR and
The synthesis and characterization of three different classes Mossbauer spectroscopy and, on the basis of these experiments,
of metal-metal-bonded metalioporphyrins have appeared in the Sn(II)-Fe(0) oxidation states have been assigned.14
literature.2,3 These classes include the following: (i) homobi- In a preliminary communication,13 the conversion of (OEP)InCl
nuclear porphyrins of the type (P)MM(P), where P is one of to (OEP)InM(L) was reported where M(L) was Co(CO)4, Mn-
several different porphyrin rings and M = Ru(II),4 Os(II),5 (CO)5, Mo(CO)3Cp, or W(CO)3Cp. The metal-metal-bonded
Mo(II),5,6 Rh(II),5,7-10 Ir(II);11 (ii) -bonded heteronuclear me- OEP derivatives were synthesized by reaction of the metálate anion
talloporphyrin complexes of the type (P)InRh(P),12 and (P)InM- with (OEP)InCl,13 and this same technique was more recently
(L);13 (iii) carbenoid-bonded heteronuclear metalioporphyrins of utilized for the synthesis of indium tetraphenylporphyrin (TPP)
the type (P)MM'(L).14-17 complexes coordinated to Mn(CO)5, Re(CO)5, Co(CO)4, and
The carbenoid complexes are typified by metalioporphyrins of Co(CO)3P(OPh)3.17
tin and germanium that are coordinated with Fe(CO)4, Mn(C- This present paper expands the number of reported metal-
0)4HgMn(CO)5, or Co(CO)3HgCo(CO)4 units.14-17 These do- metal^-bonded porphyrins and also presents a complete char-
nor-acceptor complexes have been identified by various physi- acterization of these complexes. The investigated compounds were
cochemical techniques, and X-ray structures of (OEP)SnFe- (P)InMn(CO)s, (P)InCo(CO)4, and (P)InM(CO)3Cp, where M
(CO)414 and (TPP)SnMn(CO)4HgMn(CO)517 have been pub-
=
Cr, Mo, W,18 all of which were electrochemically investigated
as to their oxidation and reduction properties. Preliminary
(1) (a) Université de Dijon, (b) Universite de Nancy I. (c) University of
Houston. electrochemistry has already been reported for reduction of two
(2) Guilard, R.; Lecomte, C.; Kadish, K. M. Struct. Bonding (Berlin), in -bonded metalioporphyrins.19 In addition, we report a novel
press. synthetic method for the preparation of several metal-metal- -
(3) Brothers, P. J.; Coliman, J. P. Acc. Chem. Res. 1986, 19, 209. bonded metalioporphyrins. This method involves reaction of a
(4) Coliman, J. P.; Barnes, C. E.; Collins, T. J.; Brothers, P. J. J. Am. bimetallic metal carbonyl complex with a -bonded alkyl- or
Chem. Soc. 1981, ¡03, 7030.
(5) Coliman, J. P.; Barnes, C. E.; Woo, L. K. Proc. Natl. Acad. Sci. U.S.A. arylindium(III) porphyrin. High yields were obtained with this
1983, 80, 7684. method, which appears to be independent of the nature of the
(6) Coliman, J. P.; Woo, L. K. Proc. Natl. Acad. Sci. V.S.A. 1984, 81, bound alkyl or aryl group. Finally, this paper describes the
2592.
molecular stereochemistry of [(2,3,7,8,12,13,17,18-octaethyl-
(7) Wayland, B. B.; Newman, A. R. Inorg. Chem. 1981, 20, 3093.
(8) Wayland, B. B.; Newman, A. R. J. Am. Chem. Soc. 1979, 101, 6472. porphyrinato)indium(III)]pentacarbonylmanganese, (OEP)-
(9) Setsune, J. L; Yoshida, Z. I.; Ogoshi, H. J. Chem. Soc., Perkin Trans. InMn(CO)5.
1 1982, 983.
(10) Ogoshi, H.; Setsune, J.; Yoshida, Z. I. J. Am. Chem. Soc. 1977, 99, Experimental Section
3869. Chemicals. Synthesis and handling of the binuclear complexes were
(11) Del Rossi, K. J.; Wayland, B. B. J. Chem. Soc., Chem. Commun. 1986, carried out under an argon atmosphere. All common solvents were
1653.
(12) Jones, N. L.; Carroll, P. J.; Wayland, B. B. Organometallics 1986, 5, thoroughly dried in an appropriate manner and were distilled under argon
33. prior to use. (TPP)InCl,20 (OEP)InCl,20 and the metálate anions21
(13) Cocolios, P.; Moise, C.; Guilard, R. J. Organomet. Chem. 1982, 228,
C43.
(14) Barbe, J.-M.; Guilard, R.; Lecomte, C.; Gerardin, R. Polyhedron 1984, (18) The investigated porphyrins, P, were OEP2" and TPP2", which represent
3, 889. the dianions of octaethylporphyrin and tetraphenylporphyrin, respec-
(15) Kadish, K. M.; Boisselier-Cocolios, B.; Swistak, C.; Barbe, J.-M.; tively.
Guilard, R. Inorg. Chem. 1986, 25, 121. (19) Cocolios, P.; Chang, D.; Vittori, O.; Guilard, R.; Moise, C.; Kadish, K.
(16) Kadish, K. M.; Swistak, C.; Boisselier-Cocolios, B.; Barbe, J.-M.; M. J. Am. Chem. Soc. 1984, 106, 5724.
Guilard, R. Inorg. Chem. 1986, 25, 4336. (20) Buchler, J. M.; Eikelman, G.; Puppe, L.; Rohbock, K.; Schneehage, H.
(17) Onaka, S.; Kondo, Y.; Yamashita, M.; Tatematsu, Y.; Kato, Y.; Goto, H.; Week, D. Justus Liebigs Ann. Chem. 1971, 745, 135.
M.; Ito, T. Inorg. Chem. 1985, 24, 1070. (21) Piper, T. S.; Wilkinson, G. J. Inorg. Nucí. Chem. 1956, 3, 104.

0020-1669/87/1326-2467S01.50/0 © 1987 American Chemical Society

2468 Inorganic Chemistry, Vol. 26, No. 15, 1987 Guilard et al.

Table I. Percent Yield and Analytical Data for (P)InM(L) Complexes

complexes, recrystn _yield, %

(P)InM(L) mol formula solvent” method A method B method C lit.6 % C % H % N % In % M

(TPP)InMn(CO)s C40H28N4InMnOs A 69 44 62.1 2.9 6.0 11.2 5.6
(63.80) (3.06) (6.07) (12.45) (5.96)
(TPP)InCo(CO)4 C4gH28N4InCo04 A/B (4/1) 20 78 85 72 63.8 3.3 5.9 12.3 5.8
(61.16) (3.14) (6.24) (12.78) (6.56)
(TPP)InCr(CO)3Cp Cs,H33N4InCr03 A/B (4/1) 30 67.9 3.8 6.1 13.2 3.5
(67.25) (3.58) (6.03) (12.36) (5.60)
(TPP)InMo(CO)3Cp C8,H„N4InMoO, A/B (4/1) 69 22 64.2 3.4 5.7 10.4 10.4
(64.22) (3.42) (5.76) (11.81) (9.86)
(TPP)InW(CO)3Cp C52H33N4InW03 A/B (4/1) 70 59.4 3.1 4.8 9.7 20.5
(58.90) (3.14) (5.28) (10.83) (17.33)
(OEP)InMn(CO)s C41H44N4InMn05 A/B (1/4) 69 59.1 5.4 6.7 13.9 5.6
(58.43) (5.26) (6.65) (13.63) (6.52)
(OEP)InCo(CO)4 C40H44N4InCoO4 A/B (1/4) 20 76 81 58.7 5.4 6.9 13.0 7.1
(58.69) (5.42) (6.84) (14.03) (7.20)
(OEP)InCr(CO)3Cp C44H49N4InCr03 A/B (1/4) 30 56.3 5.5 6.1 13.3 4.1
(62.27) (5.82) (6.60) (13.53) (6.13)
(OEP)InMo(CO)3Cp C44H49N4InMoG3 A/B (1/4) 70 29 58.2 5.5 6.1 14.3 11.2
(59.20) (5.53) (6.28) (12.86) (10.75)
(OEP)InW(CO)3Cp C44H49N4InW03 A/B (1/4) 70 54.0 4.8 5.7 11.7 18.9
(53.90) (5.04) (5.71) (11.71) (18.75)
6
Legend: A Calculated values in parentheses.
” ”
=
toluene; B =
heptane. Reference 17.

[Mn(CO)5]', [Co(CO)4]", [Cr(CO)3Cp]-, [Mo(CO)3Cp]', and [W- Table II. Experimental Conditions
(CO)3Cp]“ were synthesized by literature procedures. Reagent grade
formula C41H44N4InMnOs
methylene chloride (CH2C12, Fisher) and benzonitrile (PhCN, Aldrich)
were used for electrochemical studies and were distilled from P205 before fw 842.6
use. Tetrabutylammonium hexafluorophosphate ((TBA)PF6) was pur- space group triclinic, PI
chased from Alfa and was recrystallized from ethyl acetate/hexane cryst size, mm3 0.32 X 0.24 X 0.20
mixtures prior to use, cryst color black
lattice params
Syntheses. Three general procedures were utilized for preparation of
the dinuclear complexes. These are as follows: a, b, c, A 12.415 (3), 13.485 (2), 15.083 (3)
Method A. Solid metálate ion (0.38 mmol) was added in the dark to a, ß, y, deg 61.99 (2), 69.69 (2), 69.75 (2)
(P)InCl (0.33 mmol) in 150 mL of tetrahydrofuran. The reaction was K Z; pa¡a¡, g-cnr3 1937.3 (4); 2; 1.44
monitored by IR spectroscopy in the CO stretching region. After about q(Cu Ka), cm'1 75.79
12 h THF was evaporated at room temperature and the resulting solid diffractometer Enraf-Nonius CAD4F (room temp)
was chromatographed in the dark over a basic alumina column using a radiation Cu Ka (graphite monochromatized)
benzene/heptane mixture as eluent under an argon atmosphere. The
scan type; (sin 0)/ -26; 0.63
crude product was recrystallized from toluene/heptane. The yields for max, Á"1
this method are given in Table I and varied between 20 and 70% de- scan range, deg; scan 1 + 0.35 tan ; 0.25 <v< 0.5
pending upon the specific metálate anion. speed deg-min"1
Method B: Synthesis of (P)InCo(CO)4 and (P)InMo(CO)3Cp. Di- aperture, mm 3.2 + tan
meric Co2(CO)8 or [Mo(CO)3Cp]2 (0.38 mmol) was mixed with (P)In- hkl limits -15 < h < 15; -16 < ¿ < 16; 0 < / < 18
no. of reflcns measd 8296
(CH3) (0.33 mmol) in 150 mL of TPIF. The solution was irradiated and
the reaction monitored by taking IR spectra in the carbonyl stretching no. of reflcns used (N) 7346 (/ > 3 (/))
no. of params 468
region. The reaction was generally complete after 2 h. Purification and (7Vp)
N/Np 15.7
recrystallization of the final product were similar to that described in
method A. The yields by this method are given in Table I. program used SDP,23 SHELX24

Method C: Synthesis of (P)InCo(CO)4. Dimeric Co2(CO)8 (0.38 R(F) 0.041

0.048
mmol) was mixed with (P)InCl (0.33 mmol) in 150 mL of THF. The
reaction was complete after h as shown by IR spectroscopy. Again,
1
w 1
f[a2(F) + 0.0078F2]
the purification and recrystallization were similar to that of method A. A/°"max 0.5 (for Z of C(35))
The product yields by this method are given in Table I and were over GOF 0.81
80%. max residual density, 1.0 (on In)
Physicochemical Measurements. Elemental analyses were performed e/A3
by the “Service de Microanalyses du CNRS”. Mass spectra were re-
corded in the electron-impact mode with the Finnigan 3300 spectrometer and the counter electrode was a platinum wire. A saturated calomel
(ionizing energy 30-70 eV, ionizing current 0.4 mA, source temperature electrode (SCE) was used as the reference electrode and was separated
250-400 °C). NMR spectra were recorded at 400 MHz on a Broker from the bulk of the solution by a fritted-glass bridge. A BAS 100
WM 400 spectrometer of the Cerema (“Centre de Resonance electrochemical analyzer connected to a Houston Instruments HIPLOT
Magnetique" of the University of Dijon). Spectra were measured from DMP 40 plotter was used to measure the current-voltage curves.
5-mg solutions of the complex in C6D6 with tetramethylsilane as an Controlled-potential electrolyses were performed with an EG&G
internal reference. ESR spectra were recorded at 115 K on an IBM Model 173 potentiostat or a BAS electrochemical analyzer. Both the
Model ER 100 D spectrometer equipped with a microwave ER-040-X reference electrode and the platinum-wire counter electrode were sepa-
bridge and an ER 080 power supply. The g values were measured with rated from the bulk of the solution by means of a fritted-glass bridge.
respect to diphenylpicrylhydrazyl (g = 2.0036 ± 0.0003). Infrared Thin-layer spectroelectrochemical measurements were performed with
spectra were obtained on a Perkin-Elmer 580 B apparatus. Samples were an IBM EC 225 voltammetric analyzer coupled with a Tracor Northern
prepared as either a 1% dispersion in Csl pellets or in THF solutions. 1710 holographic optical spectrometer-multichannel analyzer to give
Electronic absorption spectra were recorded on a Perkin-Elmer 559 time-resolved spectral data. The utilized optically transparent platinum
spectrophotometer, an IBM Model 9430 spectrophotometer, or a Tracer thin-layer electrode (OTTLE) has been described in a previous publica-
Northern 1710 holographic optical spectrophotometer-multichannel an- tion.22
alyzer. For the photochemical reactions, an OSRAM HQI-T400W/DV Crystal and Molecular Structure Determination. A suitable crystal of
mercury lamp was used (power 360 W, 28 000 lm in the visible spectral (OEP)InMn(CO)5 was obtained from recrystallization of the complex

range).
Cyclic voltammetric measurements were obtained with the use of a
three-electrode system. The working electrode was a platinum button, (22) Lin, X. Q.; Kadish, K. M. Anal. Chem. 1985, 57, 1498.
Metalloporphyrins with Metal-Metal Bonds Inorganic Chemistry, Vol. 26, No. 15, 1987 2469

Table III. Fractional Coordinates, Standard Deviations, and Table IV. Mass Spectral Data of (P)InM(L) Complexes in CH2C12
Equivalent Temperature Factors (Á2) of porphyrin, P ligand, M(L) fragment m/e (%)
[(2,3,7,8,12,13,17,18-Octaethylporphyrinato)indium(III)]penta-
TPP Mn(CO)5 [(TPP)InMn(CO)5]‘+ 922 (0.7)
carbonylmanganese +
[(TPP)In] 727 (100.0)
atom X y Z B +
667
[(TPP)Mn] (3.9)
In 0.15464 (2) 0.17550 (2) 0.29003 (2) 2.624 (7) Co(CO)4 [(TPP)InCo]"1- 786 (7.9)
+
Mn 0.32822 (5) 0.30629 (5) 0.20687 (5) 3.68 (2) [(TPP)In] 727 (100.0)
Ol 0.1146 (4) 0.4743 (3) 0.2811 (4) 8.1 (2) Cr(CO)3Cp [(TPP)InCr]'+ 779 (0.6)
+
02 0.3332 (4) 0.1965 (4) 0.4278 (3) 8.5 (2) [(TPP)In] 727 (100.0)
03 0.5070 (3) 0.1119 (4) 0.1495 (4) 7.9 (2) [(TPP)Cr]+ 664 (1.3)
+
04 0.2777 (4) 0.3897 (4) 0.0075 (3) 5.7 (1) Mo(CO)3Cp [(TPP)MoCp] 773 (1.5)
+
05 0.5182 (4) 0.4483 (4) 0.1139 (4) 9.6 (2) [(TPP)In] 727 (100.0)
+
N1 -0.0317 (3) 0.2745 (2) 0.3344 (2) 3.23 (8) W(CO)3Cp [(TPP)WCp] 861 (1.4)
+
N2 0.1115 (3) 0.1868 (2) 0.1601 (2) 3.22 (8) [(TPP)In] 727 (100.0)
N3 0.2478 (3) 0.0041 (2) 0.2906 (2) 3.20 (8)
OEP 842
N4 0.1021 (3) 0.0907 (2) 0.4660 (2) 3.05 (8) Mn(CO)5 [(OEP)InMn(CO)5]'+ (0.8)
+
[(OEP)In] 647 (100.0)
COI 0.1953 (5) 0.4090 (4) 0.2532 (4) 5.4(1) 706
002 0.3318 (4) 0.2358 (4) 0.3436 (4) Co(CO)4 [(OEP)InCo]1+ (8.8)
5.4(1) [(OEP)In]
+
647 (100.0)
003 0.4374 (4) 0.1844 (4) 0.1729 (4) 5.1 (1) +
698
004 0.2966 (4) 0.3580 (4) 0.0833 (4) 4.8 (1) Cr(CO)3Cp [(OEP)InCrH] (0.3)
+
[(OEP)In] 647 (80.0)
005 0.4451 (5) 0.3934 (4) 0.1498 (4) 5.8 (2)
584
Cl -0.0891 (3) 0.2997 (3) 0.4254 (3) 3.16 (9)
[(OEP)Cr]+ (0.8)
Mo(CO)3Cp [(OEP)InMo(CO)3Cp]1+ 891 (0.3)
C2 -0.1874 (3) 0.3965 (3) 0.4107 (3) 3.5 (1)
[(OEP)MoCp]+ 808 (0.2)
C3 -0.1852 (3) 0.4281 (3) 0.3112 (3) 3.4 (1) +
647
C4 -0.0867 (3) 0.3494 (3) 0.2623 (3) 3.19 (9) [(OEP)In] (100.0)
W(CO)3Cp [(OEP)InW(CO)3Cp]’+ 980 (1.0)
C5 -0.0557 (3) 0.3500 (3) 0.1606 (3) 3.5 (1) +
[(OEP)In] 647 (100.0)
C6 0.0326 (3) 0.2733 (3) 0.1151 (3) 3.22 (9)
C7 0.0558 (8) 0.2700 (3) 0.0127 (3) 3.33 (9)
the standard deviations, and the equivalent temperature factors of the
C8 0.1529 (3) 0.1818 (3) -0.0041 (3) 3.5 (1)
C9 0.1854 (3) 0.1319 (3) 0.0892 (3) non-hydrogen atoms. Coordinates of the hydrogen atoms, thermal pa-
3.16(9) rameters (U¡j) of the non-hydrogen atoms, structure factors, bond dis-
CIO 0.2764 (3) 0.0358 (3) 0.1081 (3) 3.4(1) tances and angles in the porphyrin ligand, and a summary of least-squares
Cll 0.3024 (3) -0.0252 (3) 0.2013 (3) 3.27 (9)
-0.1293 (3) planes are given in the supplementary material.
C12 0.3905 (3) 0.2210 (3) 3.6(1)
C13 0.3883 (3) -0.1584 (3) 0.3214 (3) 3.6(1) Results and Discussion
C14 0.2968 (3) -0.0749 (3) 0.3651 (3) 3.12 (9)
Synthesis of the (P)InM(L) complexes was accomplished by
C15 0.2620 (3) -0.0783 (3) 0.4688 (3) 3.7(1) the three methods described in the Experimental Section. Method
C16 0.1720 (3) -0.0020 (3) 0.5152 (3) 2.97 (9)
C17 0.1379 (3) -0.0095 (3) 0.6246 (3) 3.19 A, which involved nucleophilic substitution of the chloride ion on
(9)
CIS 0.0473 (3) 0.0805 (3) 0.6380 (3) 3.14 (9) (P)InCl by [Mn(CO)5]-, [Co(CO)4]-, [Cr(CO)3Cp]-, [Mo-
C19 0.0247 (3) 0.1428 (3) 0.5382 (3) 2.98 (9) (CO)3Cp]-, or [W(CO)3Cp]-, was the main method of synthesis.
C20 -0.0628 (3) 0.2404 (3) 0.5183 (3) 3.24 (9) Yields by this method are summarized in Table I and suggest the
C25 -0.2665 (4) 0.4535 (4) 0.4923 (4) 4.6(1) following classification according to the metálate anion reactivity;
C26 -0.1987 (6) 0.5281 (5) 0.4920 (6) 8.2 (3)
C27 -0.2723 (4) 0.5180 (3) 0.2586 (4) 4.6(1) [Co(CO)4]“ < [Cr(CO)3Cp]~ < [Mo(CO)3Cp]- =
C28 -0.3834 (5) 0.4711 (5) 0.2843 (5) 6.9 (2) [Mn(CO)5]" < [W(CO)3Cp]"
C29 -0.0199 (4) 0.3445 (3) -0.0572 (3) 4.2(1)
C30 -0.1411 (5) 0.3031 (5) -0.0135 (4) 6.1 (2) Dessy et al.26 have reported a similar classification based on the
C31 0.2111 (4) 0.1436 (4) -0.0966 (3) 4.4 (2) nucleophilic power of the anion.
C32 0.1669 (5) 0.0389 (5) -0.0721 (4) 6.6 (2) The reaction yield could be improved by using either of two
C33 0.4636 (3) -0.1900 (3) 0.1440 (3) 4.3 (1) other synthetic methods. Method B involves a photochemical
C34 0.3877 (4) -0.2618 (4) 0.1486 (4) 5.7 (2) reaction of the aryl or alkyl -bonded porphyrin and dimeric
C35 0.4671 (4) -0.2534 (3) 0.3801 (4) 4.6(1)
C36 0.5628 (4) -0.2119 (5) 0.3847 5.6 (2)
Co2(CO)8 or [Mo(CO)3Cp]2. During this reaction the (P)In* ESR
(4) radical anion spectrum is observed. Method C was successful only
C37 0.1968 (4) -0.0979 (3) 0.7017 (3) 4.3 (1)
C38 0.3227 (5) -0.0759 (5) 0.6755 6.6 (2)
for the synthesis of (P)InCo(CO)4. This synthetic method pro-
(5)
C39 -0.0172 (4) 0.1156 (4) 0.7335 ceeds via a reaction involving (P)InCl and Co2(CO)8 in THE. The
(3) 4.0(1)
C40 0.0303 (5) 0.2157 (5) 0.7158 (4) 6.7 (2) nature of the solvent is important since the reaction was only
observed to occur in THE.
in a solution of toluene/heptane (1:4). Oscillation and Weissenberg Spectral Measurements. Elemental analysis and mass spectral
photographs along the needle axis did not reveal any symmetry. The data of the bimetallic compounds are summarized in Tables I and
experimental conditions are given in Table II. Data reduction was made IV. All of the fragmentation patterns prove the existence of a
by using the sdp package,23 and no decay was observed. No adsorption metal-metal bond in the investigated complexes. The molecular
correction was made. Fractional coordinates of the indium and manga-
nese atoms were calculated from the Patterson map. Subsequent sets of peak is of weak intensity (0.3-1%) and was observed for only a
Fourier and difference Fourier syntheses in the Pi space group then few complexes. Other fragments such as [(P)M]+ or [(P)MCp]+
revealed the whole crystal structure, including the hydrogen atoms. were also obtained and are due to a transmetalation rearrange-
These hydrogen atoms were fixed at the positions found on the Ap(r) ment. The parent peak was generally the ionic species [(P)In]+,
maps with constant isotropic temperature factors (C/(H) = 3.16 Á2). At and this suggests a relatively weak metal-metal bond.
the end of the refinement the largest residue was 1.0 e/A3 on the indium IR spectroscopic studies show that two different types of
atom. The final agreement factors are given in Table II (shelx).24 complexes can be distinguished according to the axial ligand.
Atomic scattering factors and anomalous dispersion corrections were These are the carbonylmetalate complexes and cyclopentadienyl
taken from ref 24 and 25. Table III gives the fractional coordinates,
complexes. For (P)InM(CO)3Cp compounds in solution, the local
symmetry around the axial metal is Cs, suggesting three IR- and
(23) SDP·. Structure Determination Package·, Enraf-Nonius: Delft, The Raman-active vc0 modes: 2 A' + A" (see Table V).27-32
Netherlands, 1977.
(24) Sheldrick, G. M. Programs for Crystal Structure Determination·,
University of Gottingen: Gottingen, West Germany, 1976. (26) Dessy, R. E.; Pohl, R. L.; King, R. B. J. Am. Chem. Soc. 1966, 88, 5121.
(25) International Tables for X-ray Crystallography·, Kynoch: Birmingham, (27) King, R. B.; Houk, L. W. Can. J. Chem. 1969, 47, 2959.
U.K., 1974; Yol. IV. (28) Burlitch, J. M.; Petersen, R. B. J. Organomet. Chem. 1970, 24, C65.
2470 Inorganic Chemistry, Vol. 26, No. 15, 1987 Guilard et al.

Table V. Solution" IR Data and Calculated Force Constants of (P)InM(L) Complexes

k, mdyn/A
porphyrin, P ligand, M(L) rco, cm"1 ki kb
TPP Mn(CO)5 2078 1974 15.90 15.99 0.25"
Co(CO)4 2070 1999 1970 16.76 16.00 0.334
Cr(CO)3Cp 1967 1902 1872 14.68 14.85 0.70"
Mo(CO)3Cp 1980 1905 1882 14.88 14.95 0.65"
W(CO)3Cp 1976 1898 1875 14.77 14.87 0.67"
OEP Mn(CO)$ 2075 1972 15.86 15.95 0.25"
Co(CO)4 2066 1999 1969 16.78 15.97 0.314
Cr(CO)3Cr 1963 1897 1872 14.75 14.77 0.62"
Mo(CO)3Cp 1976 1899 1882 14.76 14.93 0.63"
W(CO)3Cp 1973 1892 1877 14.65 14.87 0.65'
22
"In THF. Approximation. ck =
k¡ =
kc
=
kf -
-
h
Kt/2. dk =
kc
=
kt.'6 ek =
k¿
=
2V8
Table VI. Solid-State IR Data of (P)InM(L) Complexes"

porphyrin, P ligand, M(L) _ycQ’ cm~‘_ «'mco. cm'1 >mc. cm'1 vCHb cm'1

TPP Mn(CO)5 2078 1996 1975 1965 670 635 490

Co(CO)4 2070 1999 1973 1961 550 480
Cr(CO)3Cp 1968 1898 1870 650 580 530 1350 810
Mo(CO)3Cp 1982 1905 1878 585 520 480 1355 810
W(CO)3Cp 1979 1899 1871 580 1355 820
OEP Mn(CO)s 2071 1973 1965 669 653 490
Co(CO)4 2066 2003 1977 1950 550 545
Cr(CO)3Cp 1964 1888 1870 635 580 535 855 830
Mo(CO)3Cp 1976 1892 1874 595 495 475 855 815
W(CO)3Cp 1973 1885 1869 590 520 480 855 820
"
1% dispersion in Csl pellets. *CH stretching of the cyclopentadienyl group.

However, the general assignment is not clear-cut and must be

specified in each complex. The assignments were made by using
the calculated force constants27 summarized in Table V and also
by comparison with data from ref 28 and 29.
The two highest vibrational frequencies can be attributed to
A' modes, with A" having the lowest frequency. Moreover, the
residual charge density calculated with the middle frequency29·30
shows that a density of about 0.3 electron is localized on the
M(CO)3Cp group. Thus, these data agree well with a covalent
metal-metal bond and Graham’s coefficients31 ( , -0.94 to-1.13;
, 0.13-0.4) confirm the presence of a single covalent metal-
metal bond. In the solid state the yco bands at the lowest
wavenumber are slightly shifted (see Table VI and Figure 1).
Comparison with literature data31-35 allows assignment of the vMC0
and vMC modes. The vMco vibrations appear in the range 580-650
cm-1, and the vMC bands appear in the region 475-580 cm-1.
Bands at 820 and 1350 cm"1 (this last band is not observed for
all complexes) involve the C-H bond which is perpendicular to
the plane of the cyclopentadienyl ring.30·32,36·37
All of the infrared bands of the cyclopentadienyl group could
not be characterized because the porphyrin ring has stretching
vibrations in this same region. However, Fritz36"38 reports that
the vCH stretching bands shift to higher wavenumbers when the
metal formal oxidation state increases. Depending on the axial
ligand, a yCH shift of about 200 cm"1 is observed (between 690
and 810-830 cm"1) upon going from [M(CO)3Cp]" to (P)InM-
(CO)3Cp, and this suggests that the formal oxidation state of
indium changes from III in (P)InCl to II in (P)InM(CO)3Cp.
The local symmetry of the Co(CO)4 moiety in (P)InCo(CO)4 '/cm4
should be C3„.32·39"41 This is shown by the appearance of three Figure 1. IR spectra of (OEP)InMo(CO)3Cp recorded (a) in THF and
(b) as a 1% dispersion in Csl pellet.
(29) Kahn, O.; Bigorgne, M. J. Organomet. Chem. 1967, 10, 137. bands attributed to uco in THF solutions. The stretching and
(30) Dehand, J.; Pfeffer, M. J. Organomet. Chem. 1976, 104, 377.
(31) Graham, W. A. G. Inorg. Chem. 1968, 7, 315. bending modes of this symmetry group are 2 A, + E. Calculation
(32) Braunstein, P.; Dehand, J. Bull. Soc. Chim. Fr. 1975, 1997. of the stretching force constants (see Table V) enables assignment
(33) Parker, D. J. J. Chem. Soc. A 1970, 1382. of the highest wavenumber vibration to A[ and the lowest
(34) Parker, D- J. J Chem. Soc., Dalton Trans. 1974, 155. wavenumber vibration to E. However, more than three bands are
(35) Young, C. G.; Broomhead, J. A.; Boreham, C. J. J. Organomet. Chem.
1984, 260, 91. observed in solution (see Table VI), and this suggests a modifi-
(36) King, R. B. Inorg. Chim. Acta 1968, 2, 454.
(37) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coor-
dination Compounds, 3rd ed.; Wiley: New York, 1978; Part III, and (39) Patmore, D. J.; Graham, W. A. G. Inorg. Chem. 1966, 5, 1586.
references therein. (40) Patmore, D. J.; Graham, W. A. G. Inorg. Chem. 1967, 6, 981.
(38) Fritz, . P. Adv. Organomet. Chem. 1964, 1, 239. (41) Coffey, C. E.; Lewis, J.; Nyholm, R. S. J. Chem. Soc. 1964, 1741.
Metalloporphyrins with Metal-Metal Bonds Inorganic Chemistry, Vol. 26, No. 15, 1987 2471

Table VII. UV-Visible Data of (P)InM(L) Complexes in Benzene (X, nm; 10 3t, mol"1 L cm"1)
™ d0"3e)
Soret region
porphyrin, P ligand, M(L) I II Q bands_ e(II)/e(I)
TPP Mn(CO)s 387 (26.6) 457 (66.6) 544 (0.3) 586 (2.7) 633 (4.1) 2.50
Co(CO)4 369 (17.1) 446 (160.4) 534 (1.0) 575 (8.2) 618 (7.4) 9.38
Cr(CO)3Cp 393 (61.9) 459 (82.0) 547 (0.7) 588 (5.4) 636 (8.7) 1.32
Mo(CO)3Cp 383 (41.0) 457 (141.0) 542 (0.8) 587 (7.1) 634 (10.7) 3.44
W(CO)3Cp 374 (29.3) 456 (142.0) 546 (1.2) 587 (7.5) 634 (11.0) 4.85
OEP Mn(CO)s 377 (60.5) 449 (37.9) 560 (9.9) 593 (2.7) 0.63
Co(CO)4 370 (47.3) 435 (104.0) 553 (14.9) 588 (8.3) 2.20
Cr(CO)3Cp 378 (74.5) 451 (42.1) 564 (14.7) 594 (3.9) 0.57
Mo(CO)3Cp 372 (58.2) 448 (61.5) 563 (13.3) 595 (3.1) 1.06
W(CO)3Cp 370 (44.6) 448 (66.1) 563 (12.9) 595 (3.2) 1.48

cation of the local symmetry. The IR spectra of these complexes

have four bands in the vco region. This agrees with the Cs local
symmetry, which predicts four IR and Raman modes. The vCoCO
mode gives vibrations in the range 545-550 cm'1, and the vibration
close to 480 cm'1 for (TPP)InCo(CO)4 is attributed to the vCoC
mode.30,32
The most interesting IR spectra are obtained for the manganese
complexes. These IR spectra have two bands in the carbonyl
stretching region. The intensity of the highest wavenumber band
is much lower than the intensity of the second band. The number
of vibrations is in agreement with a C4„ local symmetry42·43 al-
though the stretching and bending modes of this group are 2 Aj
+ E. The absence of one band must result from the superposition
of A, and E modes. Such a characteristic has been already
reported,31 and calculated stretching force constants (Table V)
confirm this analysis. The carbonyl regions of the solid-state IR
spectra show a modification of the local symmetry and agree with
a Cs symmetry. Three or four bands are observed. An assignment
of i/MnC0 and vMnC modes was made: vMnC0 in the range 635-670
cm"1 and i<MnC at 490 cm"1 43-46 The small shift in frequency
between the octaethylporphyrin and tetraphenylporphyrin com-
plexes is due to the electron donor character of the octaethyl-
porphyrin macrocycle which increases the electron density on the
indium and results in a small shift of the vco bands toward lower
frequencies.
Data from the electronic absorption spectra of each complex
are summarized in Table VII. In contrast to (P)InCl, all of the
(P)InM(L) complexes have electronic absorption spectra belonging
to the hyper class.47 The Soret band involves a x —* x* electronic
transition and is red-shifted (435-459 nm) in comparison to bands
of (P)InCl complexes with the same porphyrin ring (see Figure
2). The extra absorption band in the near-UV region involves WAVELENGTH (nm)
a charge transfer from the metal to the macrocycle (a2u(npz) -*
Figure 2. UV-visible spectra of (a) (OEP)InCl and (b) (OEP)InMn-
eg(x*)). This charge transfer is induced by an increase of charge (CO)j in C6H6.
density on indium, which results from an electronic transfer be-
tween the two metals. The ratios of molar absorptivities between the indium porphyrin, and a formal In(II) oxidation state is
band II and band I are given in Table VII and indicate that this
suggested.
charge transfer is smaller than observed for alkyl or aryl -bonded The spectral properties of pure (P)InM(L) complexes are listed
indium porphyrins.48 The c(II)/e(I) ratio is smaller for the OEP in Table VII. However, another absorption band may appear in
complexes than for the TPP complexes, and this is in agreement the 400-430-nm range.17 Specifically all of the octaethyl de-
with the ring currents of each porphyrin macrocycle. rivatives may have another band at around 406 nm and all of the
The shapes of the UV-visible spectra agree with five-coordinate
tetraphenylporphyrin complexes may have an additional band at
ionic indium porphyrins. The UV-visible data show that the around 427 nm, independent of the axial ligand. These additional
properties of the indium-metal -bond in (P)InM(L) are close absorptions are of variable intensity and are not observed for all
to those of indium-carbon -bonded porphyrins. In particular, the compounds. Moreover, after irradiation by light, the intensity
a large electronic exchange occurs between the axial ligand and
of these bands increases. This is due to a decomposition of the
bimetallic complex by cleavage of the indium-metal bond, and
the absorptions at 406 or 427 nm correspond to the Soret band
(42) Cotton, F. A.; Kraihanzel, C. S. J. Am. Chem. Soc. 1962, 84, 4432. of [(P)In]+.
(43) Braunstein, P.; Dehand, J. J. Organomet. Chem. 1974, 81, 123. A !H NMR study was made on the same series of complexes
(44) Hsieh, A. T. T.; Mays, M. J. J. Chem. Soc., Dalton Trans. 1972, 516.
(45) Wilford, J. B.; Stone, F. G. A. Inorg. Chem. 1965, 4, 389. in C6D6 at ambient temperature, and the chemical shifts are
(46) Kasenally, A. S.; Lewis, J.; Manning, A. R.; Miller, J. R.; Nyholm, R. summarized in Table VIII. All of the complexes exhibit *H NMR
S.; Stiddard, . . B. J. Chem. Soc. 1965, 3407. features typical of diamagnetic metalloporphyrins.
(47) Gouterman, M. In The Porphyrins; Dolphin, D., Ed.; Academic: New The NMR spectra are analogous between the binuclear systems
York, 1978; Vol. Ill, Chapter 1, and references therein.
(48) Kadish, K. M.; Boisselier-Cocolios, B.; Cocolios, P.; Guilard, R. Inorg.. and their (P)InCl precursors. The pyrrole protons of (TPP)-
Chem. 1985, 24, 2139. InM(L) have a signal at ~9.09 ppm except for the (TPP)In-
2472 Inorganic Chemistry, Vol. 26, No. 15, 1987 Guilard et al.
Table VIII. NMR Data of (P)InCl and (P)InM(L) Complexes'
protons of
protons of R, protons of R2 axial ligand
porphyrin, P axial ligand R, r2 mult//6 mult//6 mult//6
TPP Cl C6H5 H o-H m/4 8.02 s/8 9.04
o'-H m/4 7.98
m-H 1
7.45
m/12
p-H 1

Mn(CO)s C6H5 H o-H m/4 8.35 s/8 9.09

o'-H m/4 8.07
m-HI 7.49
m/12
p-H 1

Co(CO)4 c6h5 H o-H m/4 8.54 s/8 9.30

o'-H m/4 8.32
m-HI 7.64
m/12
p-H 1

Cr(CO)3Cp c6h5 H o-H m/4 8.51 s/8 9.08 s/5 1.84

o'-H m/4 8.03
m-Hl 7.47
m/12
p-H 1
Mo(CO)3Cp c6h5 H o-H m/4 8.45 s/8 9.09 s/5 2.59
o'-H m/4 8.03
m-HI 7.47
m/12
p-H i
W(CO)3Cp C6H5 H o-H m/4 8.46 s/8 9.09 s/5 2.53
o'-H m/4 8.02
m-HI m/12 7.47
p-H I
OEP Cl H c2h5 s/4 10.39 ß-CH, t/24 1.83
a-CH2 m/8 3.88
a'-CH2 m/8 4.03
Mn(CO)5 H c2h5 s/4 10.45 0-CH3 t/24 1.88
«-CH2 m/16 4.04
Co(CO)4 H c2h5 s/4 10.48 0-ch3 t/24 1.87
a-CH2 m/16 4.03
Cr(CO)3Cp H c2h5 s/4 10.45 5-CH3 t/24 1.87 s/5 1.63
a-CH2 m/8 3.98
a'-CH2 m/8 4.08
Mo(CO)3Cp H c2h5 s/4 10.45 ß-CH, t/24 1.87 s/5 2.39
a-CH2 m/8 3.99
a’-CH2 m/8 4.09
W(CO)3Cp H C2H5 s/4 10.43 0-CH} t/24 1.87 s/5 2.35
a-CH2 m/8 3.99
a'-CH2 m/8 4.09

"Spectra recorded in C6D6 at 21 °C with SiMe4 as internal reference; chemical shifts (6) downfield from SiMe4 are defined as positive. 6Legend;
mult = multiplicity; i = intensity; s = singlet; t = triplet; m = multiple!.

Co(CO)4 complex at 9.30 ppm (see Table VIII), and this may variably appear at lower fields than those of (OEP)InCl ( =

be compared to 9.04 ppm for (TPP)InCl. No significant dif- 0.6 ppm). The meso protons give a signal close to 10.43-10.48
ferences in signal position can be observed for the other protons. ppm whereas the methylenic and methylic protons appear in the
This reflects a weak influence of the axial ligand, thus implying ranges 4.03-4.09 and 1.87-1.88 ppm (3.95 (average) and 1.83
a large distance from the nuclear center of the macrocycle. ppm for (OEP)InCl). The deshielding is attributable to the slightly
The chemical shifts of the phenyl protons give more structural higher electron-withdrawing character of the metálate anion
information. The meta and para protons have resonances in the compared to that of the chloride ion.
range 7.47-7.64 ppm. The ortho protons of (TPP)InM(L) are When the indium atom is coordinated to a [M(CO)3Cp] axial
not equivalent as is the case for (TPP)InCl.49,50 This lack of ligand, two multiplets are clearly observed for the methylenic
equivalence results in an asymmetry with respect to the porphyrin protons, and this results from a ABX3 coupling with the methylic
plane and has its origin in the symmetry of the (TPP)InM(L) protons. The difference between the resonance frequencies of the
complexes. The axial metálate ion induces a larger nonequivalence methylenic protons, |vA vB|, shows that the Cr(CO)3Cp ligand
-

of the two porphyrin faces49-52 in comparison to parameters of is the most anisotropic ligand (37.18 Hz (Mo(CO)3Cp) < 37.87
(TPP)InCl (| „/_ -

^ | = 0.04 ppm). This is due to a slower Hz (W(CO)3Cp) < 41.81 Hz (Cr(CO)3Cp)). The same clas-
rotation of the phenyl groups on the NMR time scale (| 0._ -

sification can be obtained by considering the difference between

^„| = 0.28 ((TPP)InMn(CO)5), 0.22 ((TPP)InCo(CO)4), 0.42 the two ortho proton chemical shifts of the tetraphenylporphyrin
((TPP)InMo(CO)3Cp), 0.44 ((TPP)InW(CO)3Cp), 0.48 derivatives, | 0-_ -

^. |. An ABX3 coupling is also observed

((TPP)InCr(CO)3Cp)). The ortho protons of the (TPP)InM- between the two methylenic protons of (OEP)InCo(CO)4 and
(CO)3Cp derivatives are the most inequivalent, and this can be (OEP)InMn(CO)5, but the anisotropy is smaller. This implies
attributed to a steric effect of the cyclopentadienyl group. When a small separation of indium from the plane of the porphyrin
the macrocycle is octaethylporphyrin, the resonance signals in- macrocycle. These observations are in good agreement with the
symmetry of the axial ligand; the more symmetrical the axial
(49) Abraham, R. J.; Smith, K. M. Tetrahedron Lett. 1971, 36, 3335. ligand (Cs —« C3c —* C4t), the lower the anisotropy of the methylene
(50) Janson, T. R.; Katz, J. J. In The Porphyrins·, Dolphin, D., Ed.; Aca- protons.
demic: New York, 1978; Vol. IV, Chapter 1, and references therein. The shielding of the cyclopentadienyl ligand is very strong
(51) Scheer, H.; Katz, J. J. In Porphyrins and Metalloporphyrins·, Smith,
K. M., Ed.; Elsevier Scientific: Amsterdam, 1975; Chapter 10, and compared to that in other organometallic derivatives. This
references therein. shielding is in good agreement with the ring current of the por-
(52) Busby, C. A.; Dolphin, D. J. Magn. Reson. 1976, 23, 211. phyrin macrocycle and results in a higher shielding of the protons
Metalloporphyrins with Metal-Metal Bonds Inorganic Chemistry, Vol. 26, No. 15, 1987 2473

Table IX. Bond Distances (Á), Angles (deg), and Standard

Deviations in the Coordination Polyhedron and Mn(CO)5 Ligand
In the Coordination Polyhedron
In-N(l) 2.194 (3) In-C(Ol) 3.110 (6)
In-N (2) 2.192 (4) In-C(02) 3.113 (7)
In-N(3) 2.196 (3) In-C(03) 3.110 (4)
In-N(4) 2.190 (3) In-C(04) 3.077 (4)
N(l)-N(3) 4.136 (4) N(2)-N(4) 4.115 (5)
In-Mn 2.705 (1)

N(l)-In-Mn 110.29 (9) N(l)-In-N(2) 83.3 (1)

N(2)-In-Mn 110.10 (7) N(2)-In-N(3) 83.4 (1)
N(3)-In-Mn 108.90 (8) N(3)-In-N(4) 83.5 (1)
N(4)-In-Mn 110.0 (1) N(4)-In-N(l) 83.3 (1)
In-Mn-C(Ol) 84.2 (2) In-Mn-C(02) 84.2 (2)
In-Mn-C(03) 84.0 (2) In-Mn-C(04) 82.8 (2)
In the Mn(CO)s Ligand
Mn-C(Ol) 1.834 (5) C(Ol)-Od) 1.138 (6)
Mn-C(02) 1.836 (6) C(02)-0(2) 1.129 (7)
Figure 3. ortep drawing and labeling scheme for (OEP)InMn(CO)5. Mn-C(03) 1.842 (5) C(03)-0(3) 1.130 (6)
Mn-C(C>4) 1.843 (6) C(04)-0(4) 1.127 (8)
Mn-C(C>5) 1.809 (6) C(05)-0(5) 1.134 (9)
C(01 )-Mn-C(02) 89.2 (2) C(01)-Mn-C(05) 96.3 (3)
C(01 )-Mn-C(03) 168.2 (3) C(02)-Mn-C(05) 96.2 (3)
C(02)-Mn-C(04) 167.0 (3) C(03)-Mn-C(05) 95.5 (2)
C(02)-Mn-C(03) 89.2 (2) C(04)-Mn-C(05) 96.7 (3)
C(03)-Mn-C(04) 90.1 (2) C(04)-Mn-C(01) 88.8 (2)
Mn-C(04)-0(1) 178.5 (6) Mn-C(02)-0(2) 177.4 (6)
Mn-C(03)-0(3) 177.8 (4) Mn-C(04)-0(4) 180.0 (1)

The torsional angles ( ,- - -C) of (OEP)InMn(CO)5 are

given in the supplementary material. The equatorial carbonyl
groups in (OEP)InMn(CO)s do not exactly eclipse the four In-N
bonds. The average Mn-C equatorial distance (1.839 (4) Á) is
longer than the axial one (1.809 (6) Á). This observation is in
agreement with previous structural data related to metal carbo-
nyls.54·55 Consequently, it can be deduced that the CO ligand
has a larger trans effect than the (OEP)In unit. This trans effect
Figure 4. Coordination polyhedrons of (a) (OEP)InMn(CO)s and (b) is not present for (OEP)SnFe(CO)4. The bond distances and
(OEP)SnFe(CO)4.
angles in the macrocycle agree well with those usually described
for other OEP complexes.2 The doming character of the porphyrin
on the cyclopentadienyl ligand of the more basic OEP complexes. ligand is equal to 0.07 Á. According to Wayland12 it is possible
(1.84-2.59 ppm for the TPP complexes and 1.63-2.39 ppm for to calculate the M-M' bond length of (P)MM'(P) from the in-
the OEP complexes). The smaller the metal-macrocycle distance, dividual covalent radii. If one uses the covalent radius of 1.39
the higher will be the shielding of the axial ligand protons. (For Á56 for the manganese atom and calculates an indium radius of
example, the value is 1.84 ppm for (TPP)InCr(CO)3Cp and 2.53 1.36 A from (TPP)In(CH3)57 (In-CH3 = 2.13 A, rc = 0.77 A),
ppm for (TPP)InW(CO)3Cp.) then the In-Mn single covalent bond should have a bond length
Molecular Structure Description. Figure 3 gives an ortep view of 1.39 + 1.36 = 2.75 A. This value agrees well with the ex-
of the (OEP)InMn(CO)5 complex and the numbering scheme perimental value of 2.705 (1) A.
used. Figure 4 and Table IX give the bond distances within the Reduction of (OEP)InM(L) and (TPP)InM(L). Each
coordination polyhedron. (OEP)InMn(CO)5 has two metal units, (OEP)InM(L) complex undergoes one reduction in the potential
which are linked by a single covalent bond. The In-Mn distance range of CH2C12. This is in contrast to (TPP)InM(L), which has
is 2.705 (1) Á. As expected, this metal-metal bond length is much a less basic porphyrin ring and is reduced in two single-elec-
longer than the metal-metal bond length observed in (OEP)- tron-transfer steps in CH2C12.
SnFe(CO)414 (Sn-Fe = 2.492 (1) Á). Figure 4 compares the All of the electroreductions are characterized by an instability
coordination polyhedron of the two crystal structures. Both the of the singly and doubly reduced species. This was first shown
indium and the tin atoms are five-coordinated by the porphyrin for (TPP)InM(CO)3Cp, where M = Mo, W,19 and is also true
macrocycle and the metal carbonyl unit. The average metal- for the other (P)InM(L) complexes investigated in this study.
nitrogen distances for the indium and tin compounds are 2.193 Cyclic voltammograms of (OEP)InMn(CO)5, (OEP)InMo-
(2) and 2.118 (11) Á, respectively, whereas the metal is out of (CO)3Cp, and (OEP)InCo(CO)4 are illustrated in Figure 5. The
the plane of the four nitrogens by 0.744 (1) and 0.818 (9) Á, peak current of each reduction is proportional to the square root
respectively. The manganese atom in (OEP)InMn(CO)5 is almost of the scan rate, indicating a diffusion-controlled process. A
on the fourfold axis of the porphyrin molecule (N,-In-Mn = 109.8 well-defined voltammogram with |Efa E^\ = 60 ± 10 mV is
-

± 0.9°, i = 1.4). obtained for (OEP)InMn(CO)5 and (OEP)InMo(CO)3Cp, but

The equatorial carbonyl ligands linked to the manganese or the not for (OEP)lnCo(CO)4, which undergoes a rapid cleavage of
iron atoms are bent toward the porphyrin unit in both structures the indium-metal bond after electroreduction.
((C-Mn-In> = 83.8 (5)°, (C-Fe-Sn) = 87.2 (6)°). This doming
is larger for the manganese complex and is equal to that found
in the neutron structure of HMn(CO)553 (<C-Mn-H> = 82.8 (54) Martin, M.; Rees, B.; Mitschler, A. Acta Crystallogr., Sect. B: Struct.
(8)°)· Crystallogr. Cryst. Chem. 1982, B38, 1286.
(55) Zhu, N. J.; Lecomte, C.; Coppens, P.; Keistler, J. P. Acta Crystallogr.,
Sect. B\ Struct. Crystallogr. Cryst. Chem. 1982, B38, 1286.
(56) Cotton, F. A.; Richardson, D. C. Inorg. Chem. 1966, 5, 1851.
(53) La Placa, S. J.; Hamilson, W. C.; Ibers, J. A.; Davison, J. A. Inorg. (57) Lecomte, C.; Protas, J.; Cocolios, P.; Guilard, R. Acta Crystallogr.,
Chem. 1969, 8, 1928. Sect. B\ Struct. Crystallogr. Cryst. Chem. 1980, B36, 2769.
2474 Inorganic Chemistry, Vol. 26, No. 15, 1987 Guilard et al.

a) (TPP)lnMo(CO)3Cp

b) (OEP)lnMo(CO) 3Cp

b) (TPP)lnCr(CO)3Cp /

0.00 -0.50 -1.00 -1.50

E,Volts vs SCE
Figure 5. Cyclic voltammograms for the reduction of (a) (OEP)InMn-
(CO)5, (b) (OEP)InMo(CO)3Cp, and (c) (OEP)InCo(CO)4 in CH2Cl2
containing 0.1 M (TBA)PF6. The scan rate was 0.20 V/s.

The stability of each singly reduced [(P)InM(L)]*- complex

is related to the reversibility of the reduction process at room 0.00 -0.50 -1.00 -1.50
temperature and can be estimated from the ratio of the anodic
to cathodic peak currents, which varied as a function of the M(L) E,Volts vs SCE
group bound to (TPP) In and decreased in the order Figure 6. Cyclic voltammograms of (a) (TPP)InMo(CO)3Cp and (b)
Mn(CO)5 > W(CO)3Cp > Mo(CO)3Cp > (TPP)InCr(CO)3Cp in CH2C12 containing 0.1 M (TBA)PF6 at low
Cr(CO)3Cp > Co(CO)4 temperature and at room temperature. The scan rate was 0.10 V/s.

The same order of compound stability is obtained for (TPP)- Table X. Peak Potentials (£p at 0.20 V/s) and Half-Wave Potentials
InM(L) and (OEP)InM(L). The observed trend with M(L) also (£1/2, V vs. SCE) of (P)InM(L) in CH2C12 Containing 0.1 M
follows an order of increasing nucleophilicity given for the reaction (TBA)PF6 _

of [M(L)]~ with RX.58 oxidn redn¿

Half-wave and peak potentials for the reduction of (OEP)- porphyrin, ligand,
P m(L) -1/2 -1/2
InMn(CO)5 and (TPP)InMn(CO)5 were invariant with an in-
crease in potential scan rate, but peak potentials for reduction (TPP)In none0 1.20 1.51 -1.08 -1.48
of the other (OEP)InM(L) and (TPP)InM(L) complexes shifted Mn(CO)5 0.80 1.20 1.51 -1.17 -1.62
Co(CO)4 0.91 1.01 1.20 1.52 -1.18“
by -30 mV for each 10-fold increase in scan rate. This potential 0.76 0.97 1.20 1.51 -1.23 -1.66“
shift is consistent with an irreversible chemical reaction that follows W(CO)3Cp
Mo(CO)3Cp 0.79 0.99 1.21 1.51 -1.20 -1.63“
a reversible one-electron-transfer process.59 -1.66“
Cr(CO)3Cp 0.74 1.20 1.51 -1.22“
The irreversible chemical reaction coupled to the electrore-
(OEP)In none 1.13 1.48 -1.31 -1.78
duction corresponds to a cleavage of the (P)InM(L) indium-metal -1.46
Mn(CO)5 0.76 1.13 1.47
bond, the rate of which decreases as the temperature of the solution Co(CO)4 0.82 1.01 1.13 1.48 -1.41“
is lowered. This is illustrated in Figure 6 for the reduction of 0.69 0.97 1.13 1.48 -1.49
W(CO)3Cp
(TPP)InMo(CO)3Cp and (TPP)InCr(CO)3Cp in CH2C12. Mo(CO)3Cp 0.74 0.99 1.14 1.48 -1.48
As seen in Figure 6, five anodic peaks are observed after the Cr(CO)3Cp 0.67 1.13 1.47 -1.47“
stepwise reduction of (TPP) InMo(CO) 3Cp or (TPP) InCr(CO) 3Cp “Neutral monomeric complex present as (P)InPF6. 6Corresponds to
by two electrons. Two of these peaks correspond to an oxidation oxidation of [M(L)]2. “Corresponds to reversible oxidations of (P)In-
of electrogenerated [(TPP)InM(L)]2- and [(TPP)InM(L)]*-while
PF6. ‘'Only reductions of (P)InM(L) are shown. Additional reduc-
the other three peaks can be assigned as oxidation of [(P)In]- and tions of [(P)In]+ and (P)In occur at £1/2 = -1.08 and -1.48 V (TPP)
(P)In' or the anionic metálate fragments generated upon cleavage or -1.31 and -1.78 V (OEP). “Value of at 0.20 V/s.
of the indium-metal bond.19
Peak potentials for oxidation of [(TPP)In]- and (TPP)In’ occur
Scheme I
at £p = -1.43 and -1.04 V, and anodic processes at these two
potentials are seen in Figure 6. Peak potentials for oxidation of cathodic scan (P)InM(L) ---2- [(P)InM(L)] —[(P)InM(L)]
[Mo(CO)3Cp]- and [Cr(CO)3Cp]- occur at Ep = -0.14 and -0.28 Í
V in CH2C12, and these processes are also observed in parts a and |-[M<L>3- |-[M(U3"
b of Figure 6. (P)In
‘

[( )
A decomposition of [(OEP)InCo(CO)4]'- occurs before the (P)In' + er
anodic scan [(
complex can be further reduced (see Figure 5c). The [(TPP)- (P)In' =E3= [(P)In]+ + e"
InCo(CO)4]·- derivative shows the same behavior, but a second + e-
reduction of the other (TPP)InM(L) complexes is possible. These [M(L)]" —-
1^[M(L)]2
half-wave potentials and peak potentials are listed in Table X,
and the overall reduction/oxidation sequence involving (P)InM(L)
is given in Scheme I.
(58) Dessy, R. E.; King, R. B.; Waldrop, M. J. Am. Chem. Soc. 1966, 88,
5112. The reduction of (P)InM(L) can occur by one or two electrons,
(59) Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706. depending upon the specific porphyrin ring, the temperature, and
Metalloporphyrins with Metal-Metal Bonds Inorganic Chemistry, Vol. 26, No. 15, 1987 2475
a) (TPP)lnMo(CO) 3Cp

Wavelength (nm)
Figure 8. Time-resolved electronic absorption spectra taken during ox-
idation of (TPP)InMn(CO)5 in CH2C12 containing 0.1 M (TBA)PF6.
The initial and final spectra are represented by solid lines.

Scheme II
-·" .+
(P)InM(L) = [(P)InM(L)]

I
z
;
C(P)In] + M(L)

CM (L)]+ --—-
1z2CM(L)32
Figure 7. Cyclic voltammograms for the oxidation of (a) (TPP)InMo-
(CO)3Cp, (b) (TPP)InCo(CO)4, and (c) (TPP)InMn(CO)5 in CH2C12 plexes now indicate that the site of the first electron transfer is
containing 0.1 M (TBA)PF6. The scan rate was 0.20 V/s. not that clear-cut. The reduction potentials of (P)InM(L) are
similar to potentials of the indium-carbon- -bonded complexes,48,64
the nature of the bound metálate ion. Potentials for these reactions where reduction occurs at the porphyrin ring system. Also,
are listed in Table X. Additional oxidation and reduction peaks
potential separations between the two one-electron reductions of
may also be observed for (TPP)In* and [(TPP)In]-, which are (TPP)InM(L) range between 0.40 and 0.45 V, thus further
formed after cleavage of the reduced bimetallic complex, as well
suggesting the formation of anion radicals and dianions65 before
as for [(TPP)In]+ reduction and oxidation when some decom-
cleavage of the metal-metal bond.
position of the neutral complex occurs. These potentials are not Oxidation of (P)InM(L). Cyclic voltammograms of (TPP)-
listed in Table X, but the processes are evident from the voltam-
InMo(CO)3Cp, (TPP)InCo(CO)4, and (TPP)InMn(CO)5 are
mograms in Figures 5 and 6. illustrated in Figure 7. As seen in this figure, each bimetallic
No electrochemistry of generated [M(L)]~ was observed on the
complex has one or two irreversible anodic peaks, which are
reductive potential sweep, but the oxidation of this anionic followed by two reversible processes at more positive potentials.
fragment could easily be detected on reversal of the potential. This Similar current-voltage curves were observed for oxidation of the
is evident in Figures 5 and 6, where oxidations are observed at
other (TPP)InM(L) and (OEP)InM(L) complexes, and peak
-0.22 V ([Mn(CO)5]-), -0.14 V ([Mo(CO)3Cp]-), or -0.28
=
Ep
V ([Cr(CO)3Cp]"). These processes have been identified by potentials and half-wave potentials for these processes are given
in Table X.
independent studies60-63 of these anionic species, and the oxidation The first oxidation of (P)InM(L) occurs at peak potentials
corresponds to the reaction between 0.67 and 0.91 V. This oxidation is not coupled to a reverse
reduction at any scan rate up to 200 V/s or at temperatures as
[M(L)]- —*
V2[M(L)]2 + e-
low as -78 °C. |£p £p/2| = 66 ± 4 mV and the constant ip/v]'2
-

An additional oxidation peak is also observed at Ep = -0.30 V ratio at room temperature indicate that the abstraction of one
after reduction of (TPP)InCo(CO)4. This oxidation peak is not electron is diffusion-controlled but that a rapid cleavage of the
due to [Co(CO)4]~, which is oxidized at +0.40 V, but rather to metal-metal bond follows oxidation.
oxidation of another cobalt carbonyl fragment. The electrooxidation of each (P)InM(L) complex was monitored
No evidence of an M(L) radical was detected upon decom- by variable-scan and variable-temperature electrochemistry as well
as by ESR spectroscopy and spectroelectrochemistry. A com-
position of (P)InM(L). This lack of an observed radical inter-
mediate under all experimental conditions clearly suggests the bination of results from these studies leads to the postulated
decomposition pathway shown in Scheme I. Several attempts were sequence of electron-transfer steps shown in Scheme II.
made to characterize reduced [(P)InM(L)]'- and [(P)InM(L)]2- In Scheme II, (P)InM(L) is reversibly oxidized by one electron
by spectroelectrochemical techniques. However, these spectral to give [(P)InM(L)]""1". This oxidized bimetallic complex then
methods were generally unsuccessful and only indicated mixtures undergoes a rapid cleavage of the metal-metal bond to generate
of the monomeric and bimetallic indium porphyrin in solution. [(P)In]+ and M(L)* in solution. The generated M(L) radical may
It was initially proposed that (TPP)InW(CO)3Cp was reduced dimerize to give [M(L)]260,62 or it may be oxidized directly to
at the W(CO)3Cp group,19 but combined electrochemical and [M(L)]+.
spectroelectrochemical data of several different (P)InM(L) com-
(64) Tabard, A.; Guilard, R.; Kadish, K. M. Inorg. Chem. 1986, 25, 4277.
(65) Kadish, K. M. Prog. Inorg. Chem. 1986, 34, 435-605.
(60) Kadish, K. M.; Lacombe, D. A.; Anderson, J. E. Inorg. Chem. 1986, (66) Kadish, K. M.; Cornillon, J.-L.; Cocolios, P.; Tabard, A.; Guilard, R.
25, 2246 and references therein. Inorg. Chem. 1985, 24, 3645.
(61) Pickett, C. J.; Fletcher, D. J. Chem. Soc., Dalton Trans. 1975, 879. (67) Wrighton, M. S.; Ginley, D. S. J. Am. Chem. Soc. 1975, 97, 4246.
(62) Lacombe, D. A.; Anderson, J. E.; Kadish, K. M. Inorg. Chem. 1986, (68) Lemoine, P.; Giraudeau, A.; Gross, M. Electrochim. Acta 1976, 21, 1.
25, 2074. (69) Hughey, J. L.; Bock, C. R.; Meyer, T. J. J. Am. Chem. Soc. 1975, 97,
(63) Madach, T.; Vahrenkamp, . Z. Naturforsch., B.\ Anorg. Chem., Org., 4440.
Chem. 1978, 33B, 1301. (70) Wrighton, M. Chem. Rev. 1974, 74, 401.
2476 Inorganic Chemistry, Vol. 26, No. 15, 1987 Guilard et al.

cleavage of the indium-metal bond occurs as shown in Scheme

II.
The electrochemical oxidation of [M(L)]2, where [M(L)]2 =
[Mn(CO)5]2, [Co(CO)4]2, [Cr(CO)3Cp]2, [W(CO)3Cp]2, [Mo-
(CO)3Cp]2, leads to the transient formation of an M(L) radical
after cleavage of the metal-metal bond.60,63,71 An M(L) radical
has also been obtained by a photochemical reaction,67·69·72 but its
dimerization rate constant is very high (Á:dim > 108 M-1 s-1) at
room temperature, and the species can be observed by ESR only
after trapping with 02 in solution.73-77 Thus, it is proposed that
the ESR spectrum in Figure 9 is actually due to quantities of
M(L)02" formed during the reaction of M(L)* with trace 02 in
solution.
In summary, the stability of the indium-metal-ff-bonded (P)-
InM(L) is relatively low. The neutral derivatives show some
decomposition in solution, but the magnitude of this decomposition
depends on the nature of the -bonded metálate group. In all
cases, the addition or abstraction of one electron to bimetallic
(P)InM(L) leads to a porphyrin anion or cation whose lifetime
is short and varies as a function of the axial ligand. Electrore-
duction seems to involve the porphyrin ir ring system, but par-
ticipation of a metal-based orbital cannot be ruled out.
Figure 9. ESR spectrum of oxidized (TPP)InMo(CO)3Cp at 120 K in
CH2C12 containing 0.1 M (TBA)PF6. Acknowledgment. The support of the National Science
Foundation (Grant No. CHE-8515411 and No. INT-8413696),
A direct oxidation of M(L)* to [M(L)]+ will result in increased the Robert A. Welch Foundation (K.M.K., Grant No. E-680),
oxidation currents for the first oxidation process, and this is il- and the CNRS is gratefully acknowledged. We also acknowledge
lustrated in Figure 7c for (TPP)InMn(CO)5. In contrast, for- Panos Cocolios and Dane Chang for preliminary experiments on
mation of [M(L)]2 results in an additional oxidation of this dimeric some of these systems.
species. This reaction occurs in the narrow potential range Registry No. (TPP)InMn(CO)5, 94928-90-2; (TPP)InCo(CO)4,
0.97-1.01 V (see Table X)60"63 and is illustrated by the oxidation 94943-91-6; (TPP)InCr(CO)3Cp, 108270-09-3; (TPP)InMo(CO)3Cp,
of (TPP)InMo(CO)3Cp in Figure 7a. 91312-84-4; (TPP)InW(CO)3Cp, 91312-85-5; (OEP)InMn(CO)s,
In all cases, the ultimate (P)InM(L) oxidation products after 82066-80-6; (OEP)InCo(CO)4, 82066-81-7; (OEP)InCr(CO)3Cp,
abstraction of two electrons are [(P)In]+ and [M(L)]+. The 108270-12-8; (OEP)InMo(CO)3Cp, 82496-58-0; (OEP)InW(CO)3Cp,
82496-59-1; [(OEP)In]+, 108270-13-9; (OEP)In, 108294-69-5;
[M(L)]+ cation is not further oxidized, but two reversible oxi-
dations do occur for [(P)In]+.66 Half-wave potentials for these [(TPP)In]+, 56551-52-1; (TPP)In, 102513-31-5; (OEP)InCl, 32125-07-
8; (TPP)InCl, 63128-70-1; [Mn(CO)5]-, 14971-26-7; [Co(CO)4]",
oxidations are listed in Table X, and these reactions are illustrated
14971-27-8; [Cr(CO)3Cp]-, 48121-47-7; [Mo(CO)3Cp]-, 12126-18-0;
by the voltammograms in Figure 7 for three representative [W(CO)3Cp]-, 12126-17-9; Co2(CO)8, 15226-74-1; [Mo(CO)3Cp]2,
(TPP)InM(L) complexes. 12091-64-4; (TPP)In(CH3), 63074-31-7; [(TPP)InMo(CO)3Cp]2-,
Thin-layer spectra obtained during oxidation of (TPP)InMn- 108270-14-0; [(TPP)InCr(CO)3Cp]2-, 108270-15-1; [(TPP)InMo-
(CO)5 are illustrated in Figure 8. Upon application of an oxi- (CO)3Cp]-, 108270-16-2; [(TPP)InCr(CO)3Cp]-, 108270-17-3; [(TP-
dizing potential there is rapid formation of a compound whose P)In]“, 108270-18-4; (OEP)In(CH3), 63288-51-7; In, 7440-74-6; Mn,
UV-visible spectrum has a Soret band at 425 nm, a shoulder at 7439-96-5; Co, 7440-48-4; Cr, 7440-47-3; Mo, 7439-98-7; W, 7440-33-7.
403 nm, and two Q bands at 557 and 597 nm. This spectrum Supplementary Material Available: Tables of hydrogen atom fractional
is similar to that of (TPP)InPF6. The same spectral evolution coordinates, anisotropic temperature factors, bond distances and angles
is obtained for each (P)InM(L) complex, and [(TPP)In]+ or in the porphyrin ligand, and least-squares planes and a Newman pro-
[(OEP)In]+ is the ultimate porphyrin oxidation product. Dimeric jection of the (N4)InMn(CO)5 unit along the metal-metal bond (9
pages); a table of observed and calculated structure factors for (OEP)-
Mn2(CO)10 is also formed during oxidation of (TPP)InMn(CO)5,
InMn(CO)s (45 pages). Ordering information is given on any current
and the small peak at ~340 nm in Figure 8 is attributed to this masthead page.
species.67
The above spectroelectrochemical results are in agreement with
results from cyclic voltammetry and are consistent with the (71) Madach, T.; Vahrenkamp, . Z. Naturforsch., B: Anorg. Chem., Org.
mechanism shown in Scheme II. Also, the reversible oxidation Chem. 1979, 34B, 573.
waves at +1.20 V (TPP) or +1.13 V (OEP) (Figure 7 and Table
(72) Laine, R. M.; Ford, P. C. Inorg. Chem. 1977, 16, 388.
(73) Symons, M. R.; Zimmerman, D. N. J. Chem. Soc., Dalton Trans. 1975,
X) are identical with half-wave potentials for the first and second 2545.
oxidations of (P)InPF6.66 (74) Huffadine, A. S.; Peake, B. M.; Robinson, B. H.; Simpson, J.; Dawson,
Oxidized solutions of (P)InMo(CO)3Cp have an ESR signal P. A. J. Organomet. Chem. 1976, 121, 391.

with g = 1.955 at 120 K in CH2C12 containing 0.1 M (TBA)PF6. (75) Lindsell, W. E.; Preston, P. N. J. Chem. Soc., Dalton Trans. 1979, 1105.
(76) Fieldhouse, S. A.; Fullam, B. W.; Neilson, G. W.; Symons, M. R. J.
This ESR spectrum is represented in Figure 9 and is similar to Chem. Soc., Dalton Trans. 1974, 567.
spectra reported for Mo(CO)3Cp02*.68 This again suggests that (77) Byers, B. H.; Brown, T. L. J. Am. Chem. Soc. 1977, 99, 2527.