A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2. Issue 40 (30th May 2017)

• Record Type: Journal Article
• Authors: Nakamae, Kanako; Tanaka, Miho; Kure, Bunsho; Nakajima, Takayuki; Ura, Yasuyuki; Tanase, Tomoaki
• Is Part Of: Chemistry. Volume 23:Issue 40(2017)
• Page Start: 9457
• Page End: 9461
• Publication Date: 2017-05-30
• Subjects: carbon dioxide -- copper -- diphosphine -- hydrides -- multinuclear complex; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201702071
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A copper hydride cluster [Cu8 (μ‐H)6 (μ‐dppm)5 ](PF6 )2 (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh3 )]6 with dppm in the presence of [Cu(CH3 CN)4 ]PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans ‐bicapped octahedral Cu8 framework. The Cu8 H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu3 (μ‐H)(μ‐O2 CH)(μ‐dppm)3 ]PF6, which could be developed to unprecedented hydrosilylation of CO2 catalyzed by multinuclear CuH species under mild conditions. Abstract : Copper hydride cluster : An octanuclear complex of [Cu8 (μ‐H)6 (μ‐dppm)5 ](PF6 )2 (1), was synthesized by treating [CuH(PPh3 )]6 and [Cu(CH3 CN)4 ]PF6 with bis(diphenylphosphino)methane (dppm), and showed interesting scrambling behaviors of the ligands and facile reaction with CO2 to give [Cu3 (μ‐H)(μ‐HCO2 )(μ‐dppm)3 ]PF6 (2), which led to catalytic hydrosilylation of CO2 under mild conditions.