Reactions of {Ru3(μ-PPh2)(CO)9}2(μ3:μ3-C4) with H+/H- or H2 to yield penta- and hexa-nuclear cluster compounds

Addition of K[BHBu3s] to {Ru-3 (mu -PPh2)(CO)(9)}(2) (mu (3) :mu (3)-C-4) (1), followed by acidification, is proposed to give {Ru3H(mu -PPh2)(CO)(9)}(2) (mu (3) :mu (3)-C=CHCH=C) (2), in which hydrogen atoms have added to each cluster unit and to the C-4 fragment of (1) to give a bis(vinylidene) ligand. The osmium analogue has also been prepared. In contrast, the reaction with dihydrogen results in the pentanuclear complex Ru-3 {mu (3):mu -C2C2 [Ru-2 (mu -PPh2)(CO)(6)]}(mu -PPh2)(CO)(9) (3), by cleavage of an Ru(CO)(3) fragment from (1).