Abstract
2-(Trimethylsiloxy)phenyl isocyanide (1) reacts with trans-[ReCl(N2)(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) in boiling THF to give trans-[Re(Cl)(CNC6H4-2-OSiMe3)(dppe)2] (3). In boiling CH2Cl2 the same reaction proceeds with Si−O bond cleavage to yield trans-[Re(Cl)(CNC6H4-2-OH)(dppe)2] (4). Si−O bond cleavage was also observed in the reaction of 2,6-bis(trimethylsiloxy)phenyl isocyanide (2) with trans-[ReCl(N2)(dppe)2] in boiling CH2Cl2, which yields trans-{Re(Cl)[CNC6H3(OH)2-2,6](dppe)2} (5). The Re(II) complex trans-[ReCl2(dppe)2] (6) was isolated as a side product in the above reactions. The complex mer-[ReCl3(NCCH3)(PPh3)2] reacts with 1 in CH2Cl2 to give the isocyanide complex mer-[ReCl3(CNC6H4-2-OH)(PPh3)2] (7). Complex 7 was shown by X-ray crystallography to crystallize with two molecules of chloroform per asymmetric unit. Reaction of fac-[Re(O)Cl3(SMe2)(OPPh3)] with 2 equiv of 1 leads to a Re(V) diisocyanide complex which upon Si−O bond cleavage gives the dicarbene complex fac-{Re(O)Cl...
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