CLUSTER CHEMISTRY .110. SOME COMPLEXES OBTAINED FROM REACTIONS BETWEEN M3(CO)12 (M=RU OR OS) OR RU3(MU-DPPM)(CO)10 AND 2-SUBSTITUTED TRIPHENYLPHOSPHINES AND RELATED KETO-PHOSPHINE LIGANDS

Several complexes of the type M3Ln{PR2(C6H4X)} [M3L(n) = (Ru/Os)3(CO)1 1 or Ru3(mu-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 aryl substituent X to cluster; less facile were C-C bond cleavage reactions, and P-C bond cleavages w ere not observed. Under the conditions used, the complexes Ru3(CO)11{P Ph2(C6H4X-2)} were transient intermediates in the formation of Ru3(mu- H)(mu-PPh2(C6H4(X-H)-2)}(CO)9; the analogous Ru3(mu-dppm) and Os3(mu-d ppm) complexes were more robust. Similar reactions were found for clus ters made by reaction of RU3(CO)12 and related complexes with PPh2{CH2 C(O)Ph}, in which H-migration from the ligand to the cluster results i n formation of a phosphino-enolate system. X-ray structures are report ed for the complexes Os3(CO)11{PPh2(C6H4X-2)} [X = NH2, NHC(O)Ph, CHO, CH = NNHC6H3(NO2)2-2,4], Ru3(mu-dppm) (CO)9{PPh2(C6H4X-2)} [X = NHC(O )Ph, CHO], Ru3(mu-H){mu-PPh2(C6H4Y-2)}(CO)9 [Y = NH, NC(Ph)O, N=CPh], Ru3(mu-H){mu-PPh2[C6H4NC(Ph)O-2]}(mu-dppm)(CO)7, Ru3(mu-H)(mu-dppm){mu -PPh2(C6H4NH-2)}(CO)7 and Os3(mu-H){mu-PPh2(C6H4CO-2)}(CO)9.