Dalton Gulliver T, Viau Lydie, Waterman Susan M, Humphrey Mark G, Bruce Michael I, Low Paul J, Roberts Rachel L, Willis Anthony C, Koutsantonis George A, Skelton Brian W, White Allan H
Department of Chemistry, Australian National University, Canberra ACT 0200, Australia.
Inorg Chem. 2005 May 2;44(9):3261-9. doi: 10.1021/ic050040+.
Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.
[WIr₃(μ - CO)₃(CO)₈(η - C₅Me₅)] (1c) 与 [W(C≡CPh)(CO)₃(η - C₅H₅)] 反应，以较低至中等产率得到边桥连四面体簇合物 [W₂Ir₃(μ₄ - η² - C₂Ph)(μ - CO)(CO)₉(η - C₅H₅)(η - C₅Me₅)] (3) 和边桥连三角双锥簇合物 [W₃Ir₃(μ₄ - η² - C₂Ph)(μ - η² - C=CHPh)(Cl)(CO)₈(η - C₅Me₅)(η - C₅H₅)₂] (4)。簇合物 3 通过 [W(C≡CPh)(CO)₃(η - C₅H₅)] 插入 Ir - Ir 和 W - Ir 键形成，同时伴随着配位模式从端基键合的炔基变为 μ₄ - η² 炔基配体的变化。簇合物 4 包含一个以 μ₄ - η² 方式与两个铱原子和两个钨原子相互作用的炔基配体，以及一个桥连 W - W 键的亚乙烯基配体。[WIr₃(CO)₁₁(η - C₅H₅)] (1a) 或 1c 与 [(η - C₅H₅)(CO)₂Ru(C≡C)Ru(CO)₂(η - C₅H₅)] 反应，以低产率得到 [Ru₂WIr₃(μ₅ - η² - C₂)(μ - CO)₃(CO)₇(η - C₅H₅)₂(η - C₅R₅)] [R = H (5a), Me (5c)]，对 5a 的结构研究表明其具有由 Ru 原子封顶和尖顶的 WIr₃ 蝴蝶核心；二钌乙炔基前体发生了 Ru - C 断裂，C₂ 单元插入到簇合物前体的 W - Ir 键中。[W₂Ir₂(CO)₁₀(η - C₅H₅)₂] 与二钌乙炔基试剂反应，以低产率得到 [RuW₂Ir₂{μ₄ - η² - (C₂C≡C)Ru(CO)₂(η - C₅H₅)}(μ - CO)₂(CO)₆(η - C₅H₅)₃] (6)，对 6 的结构研究表明其为一个由 Ru(η - C₅H₅) 基团封顶的蝴蝶形 W₂Ir₂ 单元，这是由 Ru - C 断裂产生的；新的钌键合丁二炔基配体的末端 C₂ 已插入到 W - Ir 键中。1a、[WIr₃(CO)₁₁(η - C₅H₄Me)] (1b) 或 1c 与 [(η - C₅H₅)(CO)₃W(C≡CC≡C)W(CO)₃(η - C₅H₅)] 反应，以高产率得到 [W₂Ir₃{μ₄ - η² - (C₂C≡C)W(CO)₃(η - C₅H₅)}(μ - CO)₂(CO)₂(η - C₅H₅)(η - C₅R₅)] [R = H (7a), Me (7c); R₅ = H₄Me (7b)]，对 7c 的结构研究表明它是 3 的金属乙炔基类似物。
