Chemical Physics Letters 402 (2005) 414–421

[Link]/locate/cplett

Characteristics of novel sandwiched beryllium, magnesium,

and calcium dimers: C5H5BeBeC5H5, C5H5MgMgC5H5,
and C5H5CaCaC5H5
Yaoming Xie a, Henry F. Schaefer III a,*
, Eluvathingal D. Jemmis b

a
Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA
b
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India

Received 29 September 2004; in final form 12 November 2004

Available online 6 January 2005

Abstract

Resa, Carmona, Gutierrez-Puebla, and Monge recently reported the synthesis and characterization of a remarkable sandwiched
di-zinc compound, Me5C5ZnZnC5Me5. Although Resa et al. emphasize that this is the first Zn(I) compound with a Zn–Zn bond, we
find the CpMMCp sandwich metal dimer bonding motif to be even more fascinating. The present theoretical studies of CpBeBeCp,
CpMgMgCp, and CpCaCaCp demonstrate that the structural pattern discovered for zinc is more generally applicable. The pre-
dicted Be–Be distance of 2.06 Å, Mg–Mg distance of 2.77 Å, and Ca–Ca distance of 3.74 Å are indicative of substantial Be–Be,
Mg–Mg, and Ca–Ca bonding. The NBO analysis shows that each metal atom has one covalent bond (to the other metal atom)
and a predominantly ionic linkage to the adjacent cyclopentadienyl ring.
Ó 2004 Elsevier B.V. All rights reserved.

1. Introduction C5H5Mg–MgC5H5, and C5H5Ca–CaC5H5. We show

here that C5H5Be–BeC5H5 (1), which can be formally
Since ferrocene was discovered in 1951, publications generated by the addition of cyclopentadienyls at the
concerning metallocenes have increased exponentially. two ends of Be2, or by the insertion of a Be atom into
The set of molecules belonging to the metallocene cat- beryllocene, is a minimum on its potential energy sur-
egory has been expanded from Ôthe compounds of a face. The electronic structure of 1 is compared to that
transition metal atom sandwiched with two cyclopenta- of cyclopentadienylberyllium hydride (2) and of beryl-
dienyl groupsÕ to Ôthose of a metal atom bonded with locene (3). Similarly, we investigate binuclear magneso-
one or more cyclopentadienyl groups (or substituents)Õ. cene, C5H5Mg–MgC5H5 (4) and its related
The recent successful synthesis [1,2] of Me5C5Zn– cyclopentadienymagnesium hydride (5) and magneso-
ZnC5Me5 has opened a new set of research targets, cene (6), as well as C5H5Ca–CaC5H5 (7) and its related
which may be called the binuclear metallocenes. Our molecules C5H5CaH (8) and C5H5CaC5H5 (9).
interest in binuclear transition metal complexes [1], C5H5Mg–MgC5H5 and C5H5Ca–CaC5H5 may be
metallocenes [3] and cyclopentadienylberyllium hydride important, because the mononuclear magnesocene
and beryllocene [4] led us to consider the electronic and calcocene are easily prepared [5,6], and they have
structure of the binuclear metallocenes containing the been widely applied as a high-purity precursor to syn-
main-group 2 elements, i.e. C5H5Be–BeC5H5, thesize important materials [7,8]. In view of the exten-
sive literature available on beryllocene, magnesocene,
*
Corresponding author. Fax: +1 706 5420406. calcocene [9], and of the important recent report [1]
E-mail address: hfs@[Link] (H.F. Schaefer III). on the synthesis and structural elucidation of

0009-2614/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/[Link].2004.11.106
 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421 415

C5Me5Zn–ZnC5Me5, our theoretical predictions invite [ad(C) = 0.75, ap(H) = 0.75]. The final contracted basis
experimental investigation. is designated Be(9s5p1d/4s2p1d), Mg(12s9p1d/6s5p1d),
Ca(14s11p3d/8s7p3d), C(9s5p1d/4s2p1d), and H(4s1p/
2s1p). All computations were carried out using the
2. Theoretical methods GAUSSIAN 94 program suite [20]. The default integra-
tion grid (75 302) was applied.
Two density functional theory (DFT) or hybrid Ha- The geometries of structures 1–9 were optimized
tree–Fock/DFT methods were used in this study. The independently with each of these DFT methods. The
first functional is B3LYP, which incorporates BeckeÕs vibrational frequencies and infrared intensities with
three parameter functional [10] (B3) with the Lee, Yang, these methods are also reported. Natural bond orbital
and Parr (LYP) [11] correlation functional. The second (NBO) analyses [21] have been carried out, with the
approach is BP86, which marries BeckeÕs 1988 exchange bond orders and natural charges used to gain some
functional (B) [12] with PerdewÕs [13] 1986 correlation understanding of the bonding in these molecules.
functional.
The basis sets employed here are of double-f plus
polarization (DZP) quality. The DZP basis set for the 3. Results and discussion
beryllium atom was composed of ThakkarÕs double-f
contraction [14] plus a set of d-type polarization func- 3.1. Binuclear beryllocene
tions [ad(Be) = 0.40]. The DZP basis set for magnesium
was composed of the McLean–Chandler double-f con- The D5h structure of C5H5–Be–Be–C5H5 (1) is opti-
traction (12s9p/6s5p) [15] plus a set of d-type polariza- mized at the B3LYP and the BP86 levels and is shown
tion functions [ad(Mg) = 0.175]. The DZP basis set for to be an energetic minimum. The energy difference
calcium was composed of the AhlrichsÕ DZDP basis between the D5d and D5h forms of C5H5–Be–Be–C5H5
set (14s11p/8s7p) [16] plus three set of d-type polariza- is less than 0.01 kcal/mol. The most interesting geomet-
tion functions [ad(Ca) = 1.3088, 0.3877, 0.1148] [17]. ric parameter for C5H5–Be–Be–C5H5 is the Be–Be dis-
The DZP basis sets for carbon and hydrogen in this tance, predicted to be 2.057 Å (B3LYP) and 2.066 Å
Letter were composed of the standard Huzinaga–Dun- (BP86), as shown on Fig. 1. These distances are compa-
ning [18,19]. double-f sets plus polarization functions rable to those found for H–Be–Be–H (2.095 or 2.113 Å)

1.425
1.433
1.428 C
1.436 C C
C C C
1.425 C
C
1.434 C C
C C
C 2.668
C 2.376 2.655
C
2.378
1.968
1.972
Ca
Mg
Be
C-H out of the ring plane C-H out of the ring plane
C-H out of the ring plane (away from the Mg atoms) (away from the Ca atoms)
(toward the Be atoms) 1.3˚ 2.1˚
2.766
3.4˚ 2.057 B3LYP 1.2˚ 2.786 1.9˚ 3.740
3.6˚ 2.066 BP86 3.734

1.550 Be
1.550
Mg

2.042 Ca
2.041
C 1.085
C 1.093 2.377
C 1,086 2.358
C
C C 1.095
C C
C 1.087
C C 1.096
C
Structure 1 C
C
C
Structure 4

Structure 7
Fig. 1. Optimized geometries for C5H5Be–BeC5H5 (1), C5H5Mg–MgC5H5 (4), and C5H5Ca–CaC5H5 (7). Bond distances are in Å.
416 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421

at the same levels of theory (Table 1). A previous theo- (BP86) indicate that there is a r bond. The charge on
retical study on HBeBeH also reported similar Be–Be each Be atom for C5H5–Be–Be–C5H5(1) is 0.849
distances (2.081–2.108 Å, at various levels of theory) (B3LYP) or 0.842 (BP86), indicating that the C5H5–Be
[22]. The Be–Be distance in structure 1 is also compara- binding in 1 is comparably ionic (per Cp ring), com-
ble with our DFT results (2.047 or 2.059 Å) for the lin- pared with the atomic charges in C5H5–Be–H(2) and
ear Cl–Be–Be–Cl (Table 1), which is the global C5H5–Be–C5H5(3) (Table 2). The C–C bond order
minimum, although a previous theoretical study re- (NLMO/NPA) of 1.32 for C5H5BeBeC5H5 is essentially
ported a rhombic Be2Cl2 structure (D2h, Cl–Cl and the same (1.32) as that for C5H5BeH. Accordingly the
Be–Be bisecting each other) [23]. All of the above Be– C–C distance of 1.425 Å (B3LYP) is comparable to
Be distances are much shorter than the experimental va- 1.428 Å found in cyclopentadienylberyllium hydride 2
lue [24] for the weakly bound diatomic Be2, namely 2.45 (C5v symmetry, Fig. 2), and to 1.425 Å for the l5 ring
Å. The highest occupied molecular orbital (HOMO) of beryllocene 3 (D5d symmetry in Fig. 3; a slipped sand-
corresponds to the Be–Be bond and there is an energy wich structure is known to lie lower in energy, but the
difference of 0.221 (B3LYP) or 0.159 a.u. (BP86) be- energy difference is quite small [4]). As for the Be–C
tween the HOMO and the LUMO. linkages, the Be–C bond order (NLMO/NPA) for
The Be–Be bond order of 0.996 (B3LYP) or 0.998 C5H5BeBeC5H5 is 0.13, which is slightly smaller than
(BP86) from the natural population analysis with natu- that of 0.16 for C5H5BeH, consistent with the prediction
ral localized molecular orbitals (NLMO/NPA) and the that the Be–C distance for C5H5BeH (1.930 Å, B3LYP)
Wiberg Be–Be bond index of 0.926 (B3LYP) or 0.924 is less than that for C5H5BeBeC5H5 (1.968 Å, B3LYP).

Table 1
M–M bond distances and bond orders for C5H5M–MC5H5, HM–MH, and ClM–MCl, (M = Be, Mg and Ca) predicted at the B3LYP and BP86
levels
B3LYP BP86 B3LYP BP86 B3LYP BP86
C5H5BeBeC5H5 (1) HBeBeH ClBeBeCl
Be–Be Distance (Å) 2.057 2.066 2.095 2.113 2.047 2.059
NLMO/NPA bond order 0.996 0.998 0.898 0.892 0.920 0.918
Wiberg bond index 0.926 0.924 0.684 0.640 0.850 0.844
C5H5MgMgC5H5 (4) HMgMgH ClMgMgCl
Mg–Mg Distance (Å) 2.776 2.786 2.862 2.884 2.772 2.788
NLMO/NPA bond order 0.957 0.956 0.741 0.719 0.901 0.893
Wiberg bond index 0.912 0.909 0.586 0.555 0.818 0.803
C5H5CaCaC5H5 (7) HCaCaH ClCaCaCl
Ca–Ca Distance (Å) 3.740 3.734 3.794 3.797 3.717 3.714
NLMO/NPA bond order 0.958 0.968 0.914 0.903 0.958 0.955
Wiberg bond index 0.934 0.932 0.726 0.696 0.921 0.916

Table 2
Atomic charges based on the natural population analysis for C5H5M–MC5H5, C5H5MH, and C5H5MC5H5 (M = Be, Mg, and Ca) predicted at the
B3LYP and BP86 levels
B3LYP BP86 B3LYP BP86 B3LYP BP86
C5H5BeBeC5H5 (1) C5H5BeH (2) C5H5BeC5H5 (3)
Atomic charge of Be 0.849 0.842 1.359 1.334 1.685 1.671
Atomic charge of C
0.401
0.407
0.400
0.407
0.395
0.402
Atomic charge of H (on ring) 0.231 0.239 0.238 0.246 0.227 0.235
Atomic charge of H (on Be)
0.546
0.527
C5H5MgMgC5H5 (4) C5H5MgH (5) C5H5MgC5H5 (6)
Atomic charge of Mg 0.922 0.912 1.464 1.433 1.842 1.830
Atomic charge of C
0.410
0.416
0.410
0.417
0.410
0.416
Atomic charge of H (on ring) 0.225 0.234 0.229 0.237 0.225 0.233
Atomic charge of H (on Mg)
0.559
0.535
C5H5CaCaC5H5 (7) C5H5CaH (8) C5H5CaC5H5 (9)
Atomic charge of Ca 0.922 0.910 1.596 1.573 1.846 1.831
Atomic charge of C
0.404
0.410
0.405
0.411
0.404
0.411
Atomic charge of H (on ring) 0.220 0.228 0.222 0.230 0.220 0.227
Atomic charge of H (on Ca)
0.678
0.665
 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421 417

2.054
2.058

1.336 B3LYP
1.349 BP86
C-H out of the ring plane
(toward the Be atom) C-H out of the ring plane Ca
(away from the Ca atom)
3.6˚ Be
3.9˚ 2.6˚
1.930 2.4˚
1.500 1.935
1.500 2.366
2.350 2.659
1.085 2.648
C C 1.093
C
C C C 1.088
1.428 C 1.096
1.436 C
C
C
Structure 2 1.693 1.426
1.706 1.434

Structure 8

Mg

2.004
2.006 2.344
C-H out of the ring plane 2.349
(away from the Mg atom)
1.4˚
1.2˚ C 1.086
C 1.095
C
C
C
1.429
1.437
Structure 5
Fig. 2. Optimized geometries for C5H5–Be–H (2), C5H5–Mg–H (5), and C5H5–Ca–H (8). Bond distances are in Å.

1.426
1.434 1.087
1.425 C C 1.096
1.433
C 1.085 C C
C 1.094 C
C
C C
2.656
2.646
2.057
2.061 C-H out of the ring plane
(away from the Ca atom)
Be 2.4˚
2.2˚ Ca
C-H out of the ring plane
(toward the Be atom) 1.662 B3LYP
1.661 BP86 1.429
6.5˚
6.8˚ 1.437 C 1.086
C 2.363
C 1.095 2.348
C C
C C
C
C
C
2.353 C C
2.357
C C
C
Structure 3
Mg
C-H out of the ring plane
2.015 (away from the Mg atom) Structure 9
2.015 1.9˚
1.6˚

C
C
C
C
C

Structure 6
Fig. 3. Optimized geometries for C5H5–Be–C5H5 (3), C5H5–Mg–C5H5 (6), and C5H5–Ca–C5H5 (9). Bond distances are in Å.
418 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421

The earlier theoretical studies on C5H5BeC5H5 and HBe–BeH þ H2 ! 2BeH2

C5H5BeH reported similar results [4] In 2003, the syn- DE ¼
13:6ðB3LYPÞ or
11:1 kcal=molðBP86Þ:
theses of derivatives of the sandwich Be(C5Me5)2 and
the related half-sandwich (g5–C5Me5)Be provide further The low exothermicities of these reactions are encour-
comparisons [25]. aging in view of the high energies of the Be–H bond in
Vibrational frequencies and infrared intensities for the relation to that of the average of the weak Be–Be and
D5h symmetry C5H5BeBeC5H5 structure at its equilib- strong H–H bonds.
rium geometry are shown in Table 3. The D5h structure The exothermic insertion reaction,
is demonstrated to be a genuine minimum by the vibra- C5 H5 BeC5 H5 þ Be ! C5 H5 BeBeC5 H5
tional analysis. In view of the recent synthesis of
DE ¼
65:5ðB3LYPÞ or
65:7 kcal=molðBP86Þ
C5He5ZnZnC5He5, it is anticipated that attempts to gen-
erate substituted variants of C5H5BeBeC5H5, C5H5Mg- demonstrates that the binuclear beryllocene is signifi-
MgC5H5, and C5H5CaCaC5H5 may also be successful. cantly more stable than beryllocene.
We have estimated the strength of the Be–Be bond
indirectly by the reactions (based on the total energies 3.2. Binuclear magnesocene
in Table 4):
The equilibrium geometry of bis-(cyclopentadienyl-
C5 H5 Be–BeC5 H5 þ H2 ! 2C5 H5 BeH magnesium) C5H5–Mg–Mg–C5H5 was predicted to have
DE ¼
14:2ðB3LYPÞ or
10:7 kcal=molðBP86Þ D5h symmetry (structure 4, Fig. 1) at both the B3LYP

Table 3
Harmonic vibrational frequencies (cm
1) and their infrared intensities (km/mol in parentheses) for C5H5Be–BeC5H5, C5H5Mg–MgC5H5, and
C5H5Ca–CaC5H5
C5H5Be–BeC5H5 C5H5Mg–MgC5H5 C5H5Ca–CaC5H5
B3LYP BP86 B3LYP BP86 B3LYP BP86
a01 171 (0) 168 (0) 128 (0) 125 (0) 88 (0) 87 (0)
770 (0) 747 (0) 453 (0) 447 (0) 320 (0) 320 (0)
956 (0) 937 (0) 788 (0) 761 (0) 771 (0) 745 (0)
1151 (0) 1123 (0) 1135 (0) 1107 (0) 1137 (0) 1109 (0)
3265 (0) 3192 (0) 3248 (0) 3175 (0) 3236 (0) 3162 (0)
a001 29 (0) 35 (0) 21 (0) 27 (0) 11 (0) 17 (0)
1272 (0) 1222 (0) 1269 (0) 1219 (0) 1269 (0) 1219 (0)
a02 1272 (0) 1222 (0) 1269 (0) 1219 (0) 1269 (0) 1219 (0)
a002 590 (43) 581 (36) 364 (154) 360 (145) 294 (149) 294 (145)
844 (649) 817 (636) 781 (630) 754 (607) 766 (681) 741 (650)
1150 (0) 1122 (0) 1134 (21) 1106 (20) 1136 (18) 1109 (15)
3265 (0) 3192 (0) 3248 (2) 3175 (3) 3236 (1) 3162 (0)
e01 70 (0) 70 (1) 38 (2) 36 (1) 23 (4) 21 (3)
390 (1) 393 (2) 242 (2) 241 (2) 233 (0) 232 (0)
808 (12) 775 (12) 761 (1) 727 (1) 754 (2) 720 (3)
1030 (32) 1001 (32) 1019 (40) 990 (40) 1019 (39) 991 (38)
1469 (4) 1421 (3) 1457 (2) 1409 (2) 1460 (1) 1413 (0)
3253 (3) 3181 (4) 3236 (7) 3162 (8) 3222 (9) 3149 (10)
e001 192 (0) 186 (0) 97 (0) 93 (0) 46 (0) 44 (0)
417 (0) 416 (0) 237 (0) 237 (0) 234 (0) 233 (0)
812 (0) 778 (0) 763 (0) 729 (0) 755 (0) 721 (0)
1031 (0) 1002 (0) 1019 (0) 990 (0) 1019 (0) 991 (0)
1470 (0) 1423 (0) 1457 (0) 1410 (0) 1460 (0) 1413 (0)
3253 (0) 3180 (0) 3236 (0) 3162 (0) 3222 (0) 3149 (0)
e02 603 (0) 582 (0) 620 (0) 600 (0) 618 (0) 596 (0)
864 (0) 837 (0) 855 (0) 825 (0) 848 (0) 818 (0)
895 (0) 855 (0) 871 (0) 833 (0) 869 (0) 831 (0)
1079 (0) 1049 (0) 1068 (0) 1039 (0) 1067 (0) 1038 (0)
1403 (0) 1367 (0) 1386 (0) 1352 (0) 1393 (0) 1360 (0)
3240 (0) 3167 (0) 3220 (0) 3147 (0) 3206 (0) 3132 (0)
e002 602 (0) 581 (0) 620 (0) 600 (0) 617 (0) 596 (0)
864 (0) 836 (0) 855 (0) 825 (0) 848 (0) 818 (0)
892 (0) 852 (0) 870 (0) 832 (0) 869 (0) 831 (0)
1078 (0) 1048 (0) 1068 (0) 1038 (0) 1067 (0) 1038 (0)
1401 (0) 1366 (0) 1386 (0) 1352 (0) 1393 (0) 1360 (0)
3240 (0) 3167 (0) 3220 (0) 3147 (0) 3206 (0) 3132 (0)
 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421 419

Table 4
Total energies (in a.u.) for C5H5Be–BeC5H5 (1), C5H5Mg–MgC5H5 (4), C5H5Ca–CaC5H5 (7) and some related molecules predicted at the B3LYP
and BP86 levels using DZP basis sets
Structure 1 Structure 2 Structure 3 HBeH HBeBeH Be H2
B3LYP
416.64514
208.92246
401.86922
15.91902
30.63917
14.67148
1.17713
BP86
416.61929
208.90583
401.85686
15.89918
30.60537
14.65775
1.17532
Structure 4 Structure 5 Structure 6 HMgH HMgMgH Mg
B3LYP
787.35541
394.25834
587.24246
201.26303
401.36122
200.09309
BP86
787.33944
394.24746
587.23152
201.25235
401.34470
200.08421
Structure 7 Structure 8 Structure 9 HCaH HCaCaH Ca
B3LYP
1742.36080
871.75975
1064.77678
678.73923
1356.32608
677.57611
BP86
1742.45425
871.80451
1064.82056
678.78431
1356.41981
677.62209

and BP86 levels, and it is shown to be a genuine minimum As for the beryllium reaction, the Mg insertion
on its potential hypersurface based on the vibrational reaction
analysis. Due to the long distance (6.9 Å) between the
two cyclopentadienyl rings and the ionic character of C5 H5 MgC5 H5 þ Mg ! C5 H5 MgMgC5 H5
the Mg–Cp bonding for structure 1, the two rings exhibit DE ¼
12:5ðB3LYPÞ or
14:9 kcal=molðBP86Þ
essentially free rotation. The energy difference between
is exothermic, and demonstrates that the formation of
the D5d and D5h forms of C5H5–Mg–Mg–C5H5 is pre-
C5H5MgMgC5H5 is favorable. The smaller absolute
dicted to be less than 0.01 kcal/mol. Therefore, experi-
value than for the beryllium analogue may be related
ments should observe C5H5–Mg–Mg–C5H5 with
to the fact that the D5h/D5d beryllocene is known to
effective D1h symmetry. The Mg–Mg distance in struc-
be very unstable.
ture 4 is predicted to be 2.766 Å (B3LYP) or 2.786 Å
Vibrational frequencies and infrared intensities for
(BP86). These are comparable to the distances found in
the D5h symmetry C5H5MgMgC5H5 structure at its
HMgMgH (2.862 or 2.884 Å) and in ClMgMgCl (2.772
equilibrium geometry are shown in Table 3. Structure
or 2.788 Å) at the same levels of theory (Table 1). A pre-
4 with D5h symmetry is confirmed to be a genuine min-
vious theoretical (SCF) study for HMgMgH and
imum on its potential hypersurface by the vibrational
ClMgMgCl also reported similar Mg–Mg distances of
analysis. However, the potential hypersurface is quite
2.920 and 2.846 Å, respectively [26]. These Mg–Mg dis-
flat, since several vibrational frequencies are very small
tances are much shorter than the experimental value for
(<100 cm
1).
the weakly bound diatomic Mg2, namely 3.890 Å [27],
We have also applied the natural bond orbital (NBO)
indicating there is significant bonding between the two
analysis to study the electronic structures of these mole-
Mg atoms in CpMgMgCp, HMgMgH, and ClMgMgCl.
cules. The Wiberg Mg–Mg bond index of 0.912
The highest occupied molecular orbital (HOMO, a01 ) cor-
(B3LYP) or 0.909 (BP86) and the NLMO/NPA Mg–
responds to the Mg–Mg bond, and there is a substantial
Mg bond order of 0.957 (B3LYP) or 0.956 (BP86)
energy difference of 0.179 (B3LYP) or 0.140 a.u. (BP86)
clearly demonstrate that there is a covalent single Mg–
between the HOMO and the LUMO.
Mg bond (Table 1). The natural atomic charge (Table
In addition, we have estimated the strength of the
2) on each Mg atom for C5H5–Mg–Mg–C5H5 (4) is
Mg–Mg bond indirectly by the following reactions
0.922 (B3LYP) or 0.912 (BP86), indicating that the
(based on the total energies in Table 4):
Mg–Cp binding in structure 4 is ionic, i.e., Cp
(Mg+–
C5 H5 Mg–MgC5 H5 þ H2 ! 2C5 H5 MgH Mg+)Cp
. Structures 5 and 6 also display Mg–Cp ionic
DE ¼ 10:0ðB3LYPÞ or 12:4 kcal=molðBP86Þ bonding based on their atomic charges (Table 2), and
they may be qualitatively depicted as Cp
Mg1.5+H0.5

HMg–MgH þ H2 ! 2MgH2 and Cp
Mg2+Cp
, respectively. Accordingly, the Wi-
berg bond index (B3LYP) for the Mg–C linkage in
DE ¼ 7:7ðB3LYPÞ or 9:6 kcal=molðBP86Þ
C5H5Mg–MgC5H5 (4) is only 0.069, and that for
Unlike the analogous exothermic reactions for C5H5MgH (5) is merely 0.034, indicating that there is al-
C5H5BeBeC5H5, these reactions for C5H5MgMgC5H5 most no covalent bonding between the magnesium and
are endothermic, demonstrating that C5H5MgMgC5H5 carbon atoms for these molecules. In the cyclopentadie-
is more stable with respect to H2 addition than C5H5Be- nyl rings, the Wiberg C–C bond index of 1.40 for
BeC5H5. Thus it is anticipated that attempts to generate C5H5MgMgC5H5 is essentially the same as that for
substituted variants of C5H5MgMgC5H5 may also be C5H5MgH. Thus, the C–C distance of 1.428 Å
successful. (B3LYP) is comparable to the 1.429 Å found in
420 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421

C5H5MgH (Fig. 2) and in magnesocene 6 (Fig. 3). The value of DE is smaller than those for the beryllium (espe-
earlier theoretical studies on the monomagnesium com- cially) and magnesium analogues.
pounds C5H5MgC5H5 and C5H5MgH reported similar Vibrational frequencies and infrared intensities for
geometries [9]. the D5h symmetry C5H5CaCaC5H5 structure at its equi-
librium geometry are shown in Table 3. Structure 7 with
3.3. Binuclear calcocene D5h symmetry is confirmed to be a genuine minimum by
the vibrational analysis. Like C5H5Be–BeC5H5 and
The mononuclear calcocene C5H5–Ca–C5H5 was pre- C5H5Mg–MgC5H5, the potential energy hypersurface
pared as early as 1956 [6]. Its crystal structure was deter- of C5H5CaCaC5H5 is also flat due to some very small
mined in 1974 [28]. There are some theoretical studies of vibrational frequencies.
calcocene [9,29]. Similar to the situations for Be and Mg The natural bond orbital (NBO) analysis was car-
analogues, it is anticipated that the binuclear calcocene ried out to study the electronic structures of C5H5Ca-
C5H5–Ca–Ca–C5H5 (structure 7), or bis-(cyclopentadie- CaC5H5 and related molecules. The Wiberg Ca–Ca
nylcalcium), might be a stable species. Our theoretical bond index of 0.934 (B3LYP) or 0.932 (BP86) and
structure (with D5h symmetry) for C5H5Ca–CaC5H5 the NLMO/NPA Ca–Ca bond order of 0.958
predicted by the B3LYP and BP86 methods is shown (B3LYP) or 0.968 (BP86) clearly demonstrate that
in Fig. 1. In fact, both D5h and D5d structures are pre- there is a covalent single Ca–Ca bond (Table 1). The
dicted to have essentially the same energy (with energy natural atomic charge (Table 2) on each Ca atom for
difference <0.01 kcal/mol). For the reasons discussed C5H5–Ca–Ca–C5H5 (7) is 0.922 (B3LYP) or 0.910
for C5H5Mg–MgC5H5, the experiments should observe (BP86), indicating that the Ca–Cp binding in structure
an effective D1h structure for C5H5Ca–CaC5H5. The 7 is ionic, i.e., Cp
(Ca+–Ca+)Cp
. Structures 8 and 9
Ca–Ca distance in structure 7 is predicted to be 3.740 also have Ca–Cp ionic bonding based on their atomic
Å (B3LYP) or 3.734 Å (BP86). These are comparable charges (Table 2), and they may be qualitatively de-
to those in HCaCaH (3.794 or 3.797 Å) and in ClCa- picted as Cp
Ca1.6+H0.6
and Cp
Ca2+Cp
, respec-
CaCl (3.717 or 3.714 Å) at the same levels of theory tively. Accordingly, the Wiberg bond index (B3LYP)
(Table 1). These Ca–Ca distances are significantly short- for the Ca–C linkage in C5H5Ca–CaC5H5 (4) is only
er than the experimental value for the weakly bound dia- 0.035, and that for C5H5CaH (5) is merely 0.033, indi-
tomic Ca2, namely 4.277 Å [27], indicating the cating that there is almost no covalent bonding be-
cyclopentadienyl groups make the Ca–Ca bonding nota- tween the magnesium and carbon atoms for these
bly stronger than that for the calcium dimer. The highest molecules. In the cyclopentadienyl rings, the Wiberg
occupied molecular orbital (HOMO, a01 ) corresponds to C–C bond index of 1.40 for C5H5Ca–CaC5H5 is essen-
the Ca–Ca bond, and there is a substantial energy differ- tially the same as that for C5H5CaH. Thus the C–C
ence of 0.109 (B3LYP) or 0.075 a.u. (BP86) between the distance of 1.425 Å (B3LYP) is comparable to the
HOMO and the LUMO. 1.426 Å found in C5H5CaH (Fig. 2) and in calcocene
Similar to our discussions on C5H5Be–BeC5H5 and 9 (Fig. 3). The earlier theoretical studies on the monoc-
C5H5Mg–MgC5H5, we have estimated the strength of alcocene C5H5CaC5H5 reported similar geometries
the Ca–Ca bond indirectly by the following reactions [9,27].
(based on the total energies in Table 4):

C5 H5 Ca–CaC5 H5 þ H2 ! 2C5 H5 CaH 4. Conclusions

DE ¼ 11:6ðB3LYPÞ or 12:9 kcal=molðBP86Þ
The D5h structures of the binuclear metallocenes
HCa–CaH þ H2 ! 2CaH2 C5H5–Be–Be–C5H5, C5H5–Mg–Mg–C5H5 and C5H5–
Ca–Ca–C5H5 are predicted to be relatively stable spe-
DE ¼ 15:5ðB3LYPÞ or 16:6 kcal=molðBP86Þ
cies. The electronic structure of these three binuclear
The DE values for these endothermic reactions are metallocenes shown by NBO analysis indicates a cova-
comparable to those reactions for C5H5MgMgC5H5. It lent single metal–metal bond and ionic bonding between
is energetically favorable for generation of the binuclear the metal (Be, Mg or Ca) and the cyclopentadienyl ring.
calcocene C5H5CaCaC5H5. The stabilizing effect of the cyclopentadienyl on the M–
Again, the insertion reaction M (M = Be, Mg, Ca) unit is significant in view of the low
dissociation energies of the isolated diatomic M2 mole-
C5 H5 CaC5 H5 þ Ca ! C5 H5 Ca
CaC5 H5 cules, namely 2.3 (Be2) [30], 1.2 (Mg2) [31], and 3.1
DE ¼
5:0ðB3LYPÞ or
7:3 kcal=molðBP86Þ kcal/mol (Ca2) [32]. The shortening of the M–M bare
dimer bonds when going to CpM–MCp is the most con-
is also exothermic, and demonstrates that the formation vincing proof of this Cp stabilizing effect. For example,
of C5H5Ca–CaC5H5 is favorable, although the absolute in diatomic Mg2 the Mg–Mg distance is 3.89 Å, while
 Y. Xie et al. / Chemical Physics Letters 402 (2005) 414–421 421

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