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Issue 32, 2019
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Tetra-, hexa- and octanuclear copper hydride complexes supported by tridentate phosphine ligands

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Abstract

Multinuclear copper hydride complexes were synthesized by using a triphosphine, bis(diphenylphosphinomethyl)phenylphosphine (dpmp). The reaction of [Cu(MeCN)4]PF6 with dpmp in 2 : 1 ratio in the presence of Me4NBH4 or NaBH4 yielded a hexanuclear complex, [Cu63-H)5(μ-dpmp)3]PF6 (1), together with a minor product [Cu8(μ-H)24-H)4(μ-dpmp)4](PF6)2 (2) in a very low yield. Complex 1 was also prepared from [CuH(PPh3)]6, [Cu(MeCN)4]PF6, and dpmp in 87%, but the yield of 2 could not be improved presumably due to its instability in solution. A tetranuclear complex, [Cu4(μ-H)(μ3-H)2(μ-dpmp)3]PF6 (4), was obtained from the reaction of [Cu(MeCN)4]PF6 with dpmp in 4 : 3 ratio, or that of [Cu3(μ-dpmp)2(MeCN)4](PF6)3 (3) and dpmp, in the presence of Me4NBH4 for both cases. The structures of 1, 2, and 4 were determined by X-ray crystallography, and the positions of hydride ligands were elucidated by DFT optimization. Complex 1 consists of a distorted trigonal anti-prismatic Cu6 core bridged by three L-shaped dpmp ligands and five μ3-hydrides, and 2 is composed of three edge-shared tetrahedral Cu4 units supported by four L-shaped dpmp ligands and two μ2-hydrides in the two outer Cu4 units and four μ4-hydride ligands in the central Cu4 units. The structures of two outer Cu4 units in 2 resemble those of 4, where a Cu4 tetrahedron is supported by two L-shaped dpmp ligands and one dpmp-κ2P,P′ bridge, in addition to one μ2- and two μ3-hydrides. Natural bond orbital analyses suggest that the hydrides act as glue between the multinuclear copper centres through electron-deficient delocalized bonding interactions, which result in partial electron migration from hydrides to CuI centres.

Graphical abstract: Tetra-, hexa- and octanuclear copper hydride complexes supported by tridentate phosphine ligands

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Publication details

The article was received on 11 Jun 2019, accepted on 18 Jul 2019 and first published on 19 Jul 2019


Article type: Paper
DOI: 10.1039/C9DT02467K
Dalton Trans., 2019,48, 12050-12059

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    Tetra-, hexa- and octanuclear copper hydride complexes supported by tridentate phosphine ligands

    T. Nakajima, K. Nakamae, R. Hatano, K. Imai, M. Harada, Y. Ura and T. Tanase, Dalton Trans., 2019, 48, 12050
    DOI: 10.1039/C9DT02467K

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