C. Tejel et al., Reversible C-H bond activation of a bifunctional phosphine bridging ligandacross two unbonded metal centers, ORGANOMETAL, 19(16), 2000, pp. 3115-3119
Reaction of [{Ir(mu-Cl)(cod)}(2)] with the short-bite bifunctional N,P-dono
r ligand (1-benzyl-2-imidazolyl)diphenylphosphine (Ph(2)PBzIm) gives the ye
llow complex [IrCl(Ph(2)PBzIm)(cod)] (2). A further addition of [{Ir(mu-Cl)
(cod)}(2)] to 2 results in the reversible metalation of a phenyl ring acros
s two unbonded iridium centers to give orange crystals of [IrCl(cod){mu-PPh
(C6H4)-(BzIm)}IrHCl(cod)] (1). Complex 1 is in equilibrium with the mononuc
lear complex [IrCl(Ph-2-PBzIm)(cod)] and the active species undergoing the
sp(2)-C-H activation, [{IrCl(cod)}(2)(mu-Ph(2)PBzIm)], in solution. Abstrac
tion of one chloride ligand from 1 with AgBF4 produces the deinsertion of t
he C-H bond yielding the cationic complex [{Ir(cod)}(2)(mu-Ph(2)PBzIm)(mu-C
l)]-BF4, which regenerates 1 upon addition of a chloride-soluble salt. The
cationic complex [{Ir-(cod)}(2)(mu-Ph(2)PBzIm)(mu-Cl)]BF4 is inactive for t
he above-mentioned sp(2)-C-H bond activation and can be prepared alternativ
ely from the reaction of 2 with [Ir(cod)(CH3CN)(2)]BF4. A related binuclear
sp(2)-C-H bond activation across two unbonded metals also occurs in the re
action of dppm with [{Ir(mu-Cl)(cod)}(2)] in a 1:1 molar ratio. This reacti
on leads to a mixture in equilibrium of [{IrCl(cod)}(2)(mu-dppm)] and the h
ydride complex [{IrCl(cod)(mu-PPh(C6H4)CH2-PPh2)}IrHCl(cod)] in a 1.5:1 mol
ar ratio, respectively, in dichloromethane at 20 degrees C. The structure o
f the mixed-valence complex 1 was solved by X-ray diffraction studies.