Gold(I) heteroatom-substituted imido complexes. Amino nitrene loss from.

The heteroatom-substituted imido complexes [(LAu)3(mu-NX)]+ (X = NR2, R = Ph, Me, Bz; X = OH, Cl; L = a phosphine) have been prepared from the reactions of NH2X with [(LAu)3(mu-O)]+. Thermally unstable [(LAu)3(mu-NNMe2)]+ (L = P(p-XC6H4)3, X = H, F, Me, Cl, MeO) decompose to the gold cluster [LAu]6(2+) and tetramethyltetrazene Me2NN=NNMe2. The decomposition is first-order overall with a rate constant that increases with increasing pKa of the phosphine ligand. Activation parameters for the decomposition are deltaH(not equal to) = 99(4) kJ/mol and deltaS(not equal to) = 18.5(5) J/K.mol for L = PPh3 and deltaH(not equal to) = 78(3) kJ/mol and deltaS(not equal to) = -47(2) J/K.mol for L = P(p-MeOC6H4)3. The decomposition of analogous [(LAu)3(mu-NNBz2)]+ produces bibenzyl, indicative of the release of free amino nitrene Bz2NN.