Facile insertion of carbon dioxide into Cu₂(μ-H) dinuclear units supported by tetraphosphine ligands.
Facile insertion of carbon dioxide into Cu₂(μ-H) dinuclear units supported by tetraphosphine ligands.
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DOI：
10.1002/asia.201402900
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发表时间：
2014-11
期刊：
影响因子：
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通讯作者：
Kanako Nakamae;B. Kure;Takayuki Nakajima;Y. Ura;T. Tanase
中科院分区：
文献类型：
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作者：
Kanako Nakamae;B. Kure;Takayuki Nakajima;Y. Ura;T. Tanase
在NaBH4存在下，中位双[（二苯基膦甲基）苯基膦]甲烷（dpmppm）与Cu(I)物质反应生成二核和四核铜氢化物配合物[Cu2(μ-H)(μ-dpmppm)2]X(1)和[Cu4(μ-H)2(μ-dpmppm)2]X (2) （X=BF4, PF6）。配合物1在室温下容易插入CO2 (1atm)，生成甲酸桥接的二铜配合物[Cu2(μ-HCOO)(dpmppm)2]X(3)。实验和DFT理论研究清楚地表明，柔性迪铜平台可以将CO2插入到Cu2（μ-H）单元中。配合物2也经过CO2插入得到甲酸桥接配合物[Cu4(μ-HCOO)3(dpmppm)2]X，在此过程中方形Cu4框架打开成线性四核链。
Reactions of meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with Cu(I) 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.