Cluster chemistry: XC. Some complexes obtained from reactions between M3(CO)12 (M = Ru or Os) or Ru3(μ-dppm)(CO)10 and 2-substituted triphenylphosphines and related keto-phosphine ligands

Abstract

Several complexes of the type M3Ln{PR2(C6H4X)} [M3Ln= (Ru/Os3(CO)11 or RU3(μ-dppm)(CO)9; X=NH2, NHCOPh, N=CHPh, CHO or CH=NNHAr, but not all combinations] have been prepared and their reactions studied. Predominant were H-migrations from the ary] substituent X to cluster; less facile were C-C bond cleavage reactions, and P-C bond cleavages were not observed. Under the conditions used, the complexes Ru3(CO)11{PPh2(C6H4X-2)} were transient intermediates in the formation of RU3(μ-H) {μ-PPh2(C6H4(X-H)-2)}(CO)9; the analogous Ru3(μ-dppm) and Os3(μ-dppm) complexes were more robust. Similar reactions were found for clusters made by reaction of RU3(CO)12 and related complexes with PPh{2{CH2C(O)Ph}}, in which H-migration from the ligand to the cluster results in formation of a phosphino-enolate system. X-ray structures are reported for the complexes Os3(CO)11{PPh2(C6H4X-2)} [X = NH2, NHC(O)Ph, CHO, CH=NNHC6H3(NO2)2-2,4], Ru3(μ-dppm) (CO)9{PPh 2(C6H4X-2)} [X = NHC(O)Ph, CHO], Ru3(μ-H)(μ-PPh2(C6H4Y-2)(CO)9 [Y = NH, NC(Ph)O, N=CPh], Ru3(μ-H) (μ-) PPh2[C6H4NC(Ph)O-2](μ-dppm)(CO)7, Ru3(μ-H)(μ-dppm)(μ-PPh2(C6H4NH-2)(CO)7 and Os3(μ-H){(μ-PPh) 2(C6H4 CO-2)}(CO)9.