The kinetics and mechanism of oxidative addition of HER3 = HSiEt3, HGeBu3, HSnBu3,
HSnPh3 to the unsaturated cluster H2Os3(CO)10, initially forming H3Os3(CO)10(ER3), are
reported. For HSiEt3 the addition is readily reversible, with an equilibrium constant of 100
M-1 at 303 K. In each case the rate law for the forward reaction is first-order in both reagents.
Rate constants (M-1 s-1) at 303 K are as follows: HSnBu3 (23) > HSnPh3 (1.5) > HGeBu3
(0.15) > HSiEt3 (3.8 × 10-3). Comparisons are made to additions of group 14 element hydrides
to 16-electron Ir(I) complexes. The reaction with HSiPh3, which forms H3Os3(CO)9(SiPh3)
and further addition products, was also examined.
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