Preparation and structural characterisation of some ruthenium cluster carbonyls containing allenylidene ligands

The chemistry of some ruthenium cluster carbonyls containing allenylidene l igands has been reinvestigated. Treatment of Ru-3(mu-H){mu(3)-C2CAr2(OH)}(C O)(9) [Ar = Ph 15, tol (tol = 4-MeC6H4)] with HBF4. OMe2 gave Ru-3(mu-H)(mu (3)-CCCAr2)(CO)(9) (Ar = Ph, R = H, Me; Ar = tol, R = H). Substitution of C O by PPh3 or dppm gave Ru-3(mu-H)(mu(3)-CCCPh2)(mu-OH)(CO)(7)(L)(2) (L = PP h3, L-2 = dppm; from 15), while in the presence of HBF4, the hydroxy-free c omplexes Ru-3(mu(3)-CCCAr2)(mu-dppm)(mu-CO)(CO)(7) were obtained. Reactions of 15 with K[BHBu3s], followed by HBF4 or AuCl(PPh3), also resulted in los s of water to give Ru-3(mu-H)(mu-E)(mu(3)-CCCPh2)(CO)(9) [E = H or Au( PPh3 ), respectively]. X-Ray structures of six of the complexes are reported.