Reactions of CO2 with tetrahydroborato copper(I) complexes in moist solvents: Synthesis and reactions of [(phen)2Cu] [(HO)3B(O2CH)] and (phen)(Ph3P)Cu(O2COH) (phen = 1,10-phenanthroline) |
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| Affiliation: | 1. Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China;2. Qianwan Institute of CNiTECH, Zhongchuangyi Road, Hangzhou Bay District, Ningbo, Zhejiang 315336, China;3. Department of Chemistry, University of North Carolina Chapel Hill, Chapel Hill, NC 27599, USA;4. Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China |
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| Abstract: | Carbon dioxide reacts with the tetrahydroborato copper(I) complex, (phen)(Ph3P)Cu(BH4) (phen = 1,10-phenanthroline) (1) in moist tetrahydrofuran and in the presence of free phen affording the ionic derivative [(phen)2Cu] [(HO)3B(O2CH)] (3). The same complex 3 can be obtained from 1 and aqueous formic acid in the presence of phen; from the new tetrahydroborato copper(I) complex, (phen)2Cu(BH4) (2), and aqueous formic acid; and from 2 with CO2 in moist tetrahydrofuran.The reaction of (phen)(Ph3P)Cu(BH4) (1) with CO2 in moist methanol gives the bicarbonato derivative, (phen)(Ph3P)Cu(O2COH) (4). The action of alcohols, ROH, on 3 causes the formation of the ionic formato complex [(phen)2Cu](O2CH) (5), the boron atom being eliminated as the alkyl boric ester, (RO)3B. Complex 3 reacts with an alcoholic triphenylphosphine solution giving the already reported covalent formato derivative, (phen)(Ph3P)Cu(O2CH). The reaction of 3 with PhCH2Br gives the benzyl formic ester HCO2CH2Ph. The reactivity of 4 toward neutral ligands such as phen and CyNC has been investigated, the ionic bicarbonato derivatives, [(phen)2Cu](HCO3) (8) and [(phen)(CyNC)2Cu](HCO3) (9), being obtained respectively. |
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