Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands |
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| Authors: | Kanako Nakamae Dr. Bunsho Kure Prof. Takayuki Nakajima Prof. Yasuyuki Ura Prof. Tomoaki Tanase |
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| Affiliation: | Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya‐nishi‐machi, Nara, 630‐8506 (Japan), Fax: (+81)?742‐20‐3847 |
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| Abstract: | Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with CuI species in the presence of NaBH4 afforded di‐ and tetranuclear copper hydride complexes, [Cu2(μ‐H)(μ‐dpmppm)2]X ( 1 ) and [Cu4(μ‐H)2(μ4‐H)(μ‐dpmppm)2]X ( 2 ) (X=BF4, PF6). Complex 1 undergoes facile insertion of CO2 (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu2(μ‐HCOO)(dpmppm)2]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO2 insertion into the Cu2(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO2 insertion to give a formate‐bridged complex, [Cu4(μ‐HCOO)3(dpmppm)2]X, during which the square Cu4 framework opened up to a linear tetranuclear chain. |
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| Keywords: | CO2 insertion copper hydride complex dinuclear complex formate complex tetraphosphine ligand |
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