Transition metal
isocyanide
complexes
Transition metal isocyanide complexes
are coordination compounds containing
isocyanide ligands. Because isocyanides
are relatively basic, but also good pi-
acceptors, a wide range of complexes are
known. Some isocyanide complexes are
used in medical imaging.
Technetium (99mTc) sestamibi is used
in nuclear medicine imaging.[1]
Scope of isocyanide ligands
structure of Os3(CO)9(CNCH2)3CMe.[2]
Several thousand isocyanides are known,
but the coordination chemistry is
dominated by a few ligands.[3] Common
isonitrile ligands are methyl isocyanide,
tert-butyl isocyanide, phenyl isocyanide,
and cyclohexylisocyanide.
Isocyanides are electronically similar to
CO, but for most R groups, isocyanides are
superior Lewis bases and weaker pi-
acceptors. Trifluoromethylisocyanide is
the exception, its coordination properties
are very similarly to those of CO.
Because the CNC linkage is linear, the
cone angle of these ligands is small, so it
is easy to prepare polyisocyanide
complexes. Many complexes of
isocyanides show high coordination
numbers, e.g. the eight-coordinate cation
[Nb(CNBu−t)6I2]+.[4] Very bulky isocyanide
ligands are also known, e.g. C6H3-2,6-Ar2-
NC (Ar =aryl).[5]
Di- and triisocyanide ligands are well
developed, e.g., (CH2)n(NC)2. (CH2)n((NC)2.
Usually steric factors force these ligands
to bind to two separate metals, i.e., they
are binucleating ligands.[6] Chelating
diisocyanide ligands require elaborate
backbones.[7]
Synthesis
Structure of Fe(tert-BuNC)5. Notice
that some C-N-C angles strongly
deviate from 180°, a characteristic of
low-valent isocyanide complexes.[8]
Because of their low steric profile and high
basicity, isocyanide ligands often install
easily, e.g. by treating metal halides with
the isocyanide. Many metal cyanides can
be N-alkylated to give isocyanide
complexes.[9]
Reactions
Typically, isocyanides are spectator
ligands, but their reduced and oxidized
complexes can prove reactive by virtue of
the unsaturated nature of the ligand
The first metal carbene complex, Chugaev's red salt, was not
recognized as such until decades after its preparation.[10]
Cationic complexes are susceptible to
nucleophilic attack at carbon. In this way,
the first metal carbene complexes where
prepared. Because isocyanides are both
acceptors and donors, they stabilize a
broader range of oxidation states than
does CO. This advantage is illustrated by
the isolation of the homoleptic vanadium
hexaisocyanide complex in three oxidation
states, i.e., [V(CNC6H3-2,6-Me2)6]n for n =
-1, 0, +1.[11]
Because isocyanides are more basic
donors ligands than CO, their complexes
are susceptible to oxidation and
protonation. Thus, Fe(tBuNC)5 is easily
protonated, whereas its counterpart
Fe(CO)5 is not:[8]
Fe(CNR)5 + H+ → [HFeL5]+
Fe(CO)5 + H+ → no reaction
Some electron-rich isocyanide complexes
protonate at N to give aminocarbyne
complexes:[12]
LnM-CNR + H+ → [LnM≡CN(H)R]+
Isocyanides sometimes insert into metal-
alkyl bonds to form iminoacyls.[13]
Structure and bonding
Isocyanide complexes often mirror the
stoichiometry and structures of metal
carbonyls. Like CO, isocyanides engage in
pi-backbonding. The M-C-N angle provides
some measure of the degree of
backbonding. In electron-rich complexes,
this angle is usually deviates from 180°.
Unlike CO, cationic and dicationic
complexes are common. RNC ligands are
typically terminal, but bridging RNC ligands
are common. Bridging isocyanides are
always bent. General trends can be
appreciated by inspection of the
homoleptic complexes of the first row
transition metals.
