447402-72-4Relevant academic research and scientific papers
Perpendicular to parallel reorientation of a terminal alkyne on a mixed-metal triangle; synthesis and structural characterisation
Mays, Martin J.,Raithby, Paul R.,Sarveswaran, Koshala,Solan, Gregory A.
, p. 1671 - 1677 (2002)
Reaction of [Fe2(CO)6(μ-η2-CCPh)(μ-PPh 2)]1 with [W2(CO)4(η5-C5H5) 2] affords the coordinatively unsaturated 46-electron trinuclear Fe2W cluster [Fe2W(CO)5(η5-C5H 5){μ3-η2-(⊥)-HCCPh}(μ-CO) (μ-PPh2)]2, in which an Fe-W edge is perpendicularly-bridged by a terminal alkyne molecule. Treatment of 1 with [Mo2(CO)4(η5-C5H 5)2] also gives a 46-electron cluster, [Fe2Mo(CO)5(η5-C5H 5){μ3-η2-(⊥)-HCCPh}(μ-CO) (μ-PPh2)]3, the molybdenum analogue of 2 and, in addition, the saturated 48-electron FeMo2 trinuclear cluster [FeMo2(CO)5(η5-C5H 5)2{μ3-η2-(⊥)-CCPh}- (μ-PPh2)]4, in which an acetylide ligand perpendicularly bridges an Fe-Mo bond. The trimetallic FeWCo acetylide-bridged species, [FeWCo(CO)6(η5-C5H5){μ 3-η2-(⊥)-CCPh}(μ-PPh2)]5, is the unique product when 1 is treated with the WCo heterobimetallic complex [CoW(η5-C5H5)(CO)7], while the corresponding reaction of 1 with [CoMo(η5-C5H5)(CO)7], leads to 3 and the molybdenum analogue of 5, [FeMoCo(CO)6(η5-C5H5){μ 3-η2-(⊥)-CCPh}(μ-PPh2)]6. Carbonylation of 3 at elevated pressure (80 atm CO) results in a ⊥-∥ alkyne reorientation to give the 48-electron cluster, [Fe2Mo(CO)6(η5-C5H 5){μ3-η2-(∥)-HCCPh}(μ-CO) (μ-PPh2)]7, as the sole product. Conversion of 7 back to 3 has been shown to occur in solution at room temperature. Single crystal X-ray diffraction studies have been performed on 2, 3, 4, 6 and 7.
