Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(¦Ç⁵-C₅Me₅)(NCMe)₃]²⁺ Dication as a Building Block

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• 作者：Saifun Nahar ; John E. Davies ; Gregory P. Shields and Paul R. Raithby
• 关键词：Cluster carbonyl ; Rhodium ; Osmium ; Ruthenium ; Cyclopentadienyl ; X ; ray crystal structure
• 刊名：Journal of Cluster Science
• 出版年：2010
• 出版时间：September 2010
• 年：2010
• 卷：21
• 期：3
• 页码：379-396
• 全文大小：343.5 KB

文摘

Reaction of the [Rh(η5-C₅Me₅)(NCMe)₃]2+ (1) dication with the hexaosmium [Os₆(CO)₁₇]2− (2) dianion leads to the initial formation of [Os₆(CO)₁₇Rh(η5-C₅Me₅)] (3). This cluster readily adds CO to form [Os₆(CO)₁₈Rh(η5-C₅Me₅)] (4) which has been characterised crystallographically. 3 also adds dihydrogen to give [Os₆H₂(CO)₁₇Rh(η5-C₅Me₅)] (5) and undergoes a substitution reaction with PPh₃ to form [Os₆(CO)₁₆(PPh₃)Rh(η5-C₅Me₅)] (6). With the [Ru₆(CO)₁₈]2− (7) dianion, [Rh(η5-C₅Me₅)(NCMe)₃]2+ (1) reacts to form three mixed-metal clusters [Ru₅(CO)₁₅Rh(η5-C₅Me₅)] (8), [Ru₆(CO)₁₈Rh(η5-C₅Me₅)] (9) and [Ru₆(CO)₁₈Rh₂(η5-C₅Me₅)₂] (10). The clusters have been characterised spectroscopically and the structures of 8 and 10 have been confirmed crystallographically. The cluster 8 undergoes a substitution reaction with P(OMe)₃ to form the disubstituted product [Ru₅(CO)₁₃(P(OMe)₃)₂Rh((η5-C₅Me₅)] (11) which has also been characterised crystallographically.