Reaction of [Wlr(3)(mu-CO)(3)(CO)(8)(eta-C5Me5)] (1c) with [W(C equivalent to CPh)(CO)(3)(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W(2)vertical bar r(3)(mu(4)-eta(2)-C2Ph)(mu-CO)(CO)(9)(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W(3)vertical bar r(3)(mu(4)-eta(2) -C2Ph)(mu-eta(2)-C=CHPh)(Cl)(CO)(8)(eta-C5Me5)(eta-C5H5)(2)] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C equivalent to CPh)(COi(3)(eta-C5H5))] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu(4) - eta(2) alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu(4)-eta(2) fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [Wlr(3)(CO)(11)(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)(2)Ru(C equivalent to C)RU(CO)(2)(eta-C5H5)] afforded [Ru(2)Wlr(3)-(mu(5)-eta(2) C-2)(mu-CO)(3)(CO)(tau)(eta-C5H5)(2)(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a Wlr(3) butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C-2 unit into a W-Ir bond of the cluster precursor. Reaction of [W(2)lr(2)(CO)(10)(eta-C5H5)(2)] the diruthenium ethyndiyl reagent gave [RuW(2)lr(2){mu(4)-eta(2-)(C2C equivalent to C)Ru(CO)(2)(eta-C5H5)(3)](tt-CO)2(CO)6(q-C5H5)31 (6) in low yield, a structural study of 6 revealing a butterfly W(2)lr(2) unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C-2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between la, [Wlr(3)(CO)(11)(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)(3)W(C equivalent to CC equivalent to C)W(CO)(3)(eta-C5H5)] afforded [W(2)lr(3){mu(4)-eta(2-) (C2C equivalent to C)W(CO)(3)(eta-C5H5)}(mu-CO)(2)(CO)(2)(n-C5H5)(q-C5R5)] [R = H (7a), Me (7c), 5 H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.