Abstract
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.
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