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• W2072380665 endingPage "971" @default.
• W2072380665 startingPage "958" @default.
• W2072380665 abstract "The complex [Ru(THF)(CO)2(η5-7,8-C2B9H11)] (1a, THF = tetrahydrofuran) reacts with the alkylidyne reagents [M(⋮CC6H4Me-4)(CO)2(η5-C5H5)] (M = Mo or W) to give the compounds [MRu(μ-CC6H4Me-4)(CO)4(η5-7,8-C2B9H11)(η5-C5H5)] (M = W (2a), Mo (2b)), which readily isomerize to the species [MRu(CO)4{σ,η5-9-CH(C6H4Me-4)-7,8-C2B9H10}(η5-C5H5)] (M = W (3a), Mo (3b)). The structure of 3b was established by X-ray diffraction. The Mo(CO)2(η5-C5H5) fragment is attached to the closo-RuC2B9 framework by a Mo−Ru bond and a three-center two-electron B−H⇀Mo linkage involving a boron atom in an α site in the CCBBB ring ligating the ruthenium. The CH(C6H4Me-4) moiety bridges between the Ru(CO)2 group and the B atom located in the other α site in the CCBBB ring. The oxo complex [WRuO{μ-σ,η5-9-CH(C6H4Me-4)-7,8-C2B9H10}(CO)2(η5-C5H5)] (4a) is a side product in the formation of 3a, and it also was characterized by X-ray diffraction. Treatment of the species 3 with PMe3 affords the zwitterionic compounds [MRu(CO)4{η5-9-CH(PMe3)(C6H4Me-4)-7,8-C2B9H10}(η5-C5H5)] (M = W (5a), Mo (5b)). A single-crystal X-ray diffraction study of 5a revealed that the (OC)2W−Ru(CO)2 unit is bridged by the nido-9-CH(PMe3)(C6H4Me-4)-7,8-C2B9H10 group. The open C2B3 face is pentacoordinated to the Ru atom, and there is an exopolyhedral B−H⇀W bond involving a Bα atom in the CCBBB ring. The other Bα site carries the CH(PMe3)(C6H4Me-4) substituent. Reactions between the ruthenium reagent [Ru(THF)(CO)2(η5-7,8-Me2-7,8-C2B9H9)] (1b) and [W(⋮CC6H4Me-4)(CO)2(η5-C5H5)] gave [WRuO{μ-σ,η5-7,8-Me2-10-CH(C6H4Me-4)-7,8-C2B9H8}(CO)2(η5-C5H5)] (4b), [WRu(μ-H){μ-η5,η‘5-7,8-Me2-9-C5H4-10-CH2(C6H4Me-4)-7,8-C2B9H7}(CO)5] (6a), and [WRu{μ-σ,η5-2,7-Me2-8-CH2(C6H4Me-4)-9-C(H)O-2,7-C2B9H6}(CO)4(η5-C5H5)] (7a) that were separated by column chromatography. The corresponding reaction between 1b and [W(⋮CC6H4Me-2)(CO)2(η5-C5H5)] afforded [WRuO{μ-σ,η5-7,8-Me2-n-CH(C6H4Me-2)-7,8-C2B9H8}(CO)2(η5-C5H5)] (n = 9 (4c), 10 (4d)) and [WRu{μ-σ,η5-2,7-Me2-8-CH2(C6H4Me-2)-9-C(H)O-2,7-C2B9H6}(CO)4(η5-C5H5)] (7b). Treatment of 1b with [Mo(⋮CC6H4Me-n)(CO)2(η5-C5H5)] (n = 4 or 2) yielded [MoRu(μ-H){μ-η5,η‘5-7,8-Me2-9-C5H4-10-CH2(C6H4Me-n)-7,8-C2B9H7}(CO)5] (n = 4 (6b), 2 (6c)). The structures of 4b, 6b, and 7b were established by X-ray diffraction. In 6b, the (OC)3Mo(μ-H)Ru(CO)2 unit is bridged by a 7,8-Me2-9-C5H4-10-CH2(C6H4Me-4)-7,8-C2B9H7 moiety, a structure resulting from a linking of C5H5 and nido-C2B9 groups. The C5 ring is η5-coordinated to the molybdenum, while the open CCBBB face of the carborane cage is similarly attached to the ruthenium. In complex 7b, a nido-2,7-Me2-8-CH2(C6H4Me-2)-9-C(H)O-2,7-C2B9H6 cage system bridges the Ru−W bond with an η5-CB4 ring coordinated to the Ru atom and with the cage joined to the W atom by a B−W bond. In addition, the C(H)O group forms a second bridge linking the cage to the tungsten, with the latter coordinated by the formyl O atom." @default.
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• W2072380665 date "1997-03-01" @default.
• W2072380665 modified "2023-09-24" @default.
• W2072380665 title "Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten" @default.
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• W2072380665 doi "https://doi.org/10.1021/om960928t" @default.
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