Acetylide generation and coupling on electron-rich Ru_3 clusters

摘要

Thermolysis of [Ru_3(CO)_10(Ph_2PC ident to CBu~t)_2] (la) gives the 48-e cluster [Ru_3(mu-eta~1, eta~2-C ident to CBu~t)2(mu-PPh_2)_2(CO)_6] (4), which readily adds CO or PPh_3 to give the corresponding 50-e clusters [Ru_3(mu-eta~1, eta~2-C ident to CBu~t)_2(mu-PPh_2)_2(CO)_6(L)] (L = CO, 5a, PPh_3, 6) while thermolysis of [Ru_3(CO)_10(Ph_2PC ident to CPh)(Ph_2PC ident to CR)] (R = Ph, 1b; Bu~t 1c) affrods 50-e [Ru_3(mu-PPh_2)(mu-eta~1, eta~2-C ident to CPh)(mu-eta~1,eta~2-C ident to CR)(CO)_7] (5b, 5c) directly, which convert smoothly to the 48-e diyne clusters [Ru_3(mu-eta~2-PhC_2C ident to CR)(mu-PPh_2)_2(CO)_7] (7b, 7c). In the case of [Ru_3(CO)_10(Ph_2PC ident to CPh)_2] the compound {Ru_2[eta~1,eta~1:eta~2,eta~2-PhCC(PPh_2)CCPh](CO)_5}(mu-PPh_2)[Ru(CO)_3] (8) is also obained.