Facially Dispersed Polyhydride Cu 9 and Cu 16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks

Autor: Yasuyuki Ura, Yasutaka Kitagawa, Tomoaki Tanase, Kanako Nakamae, Takayuki Nakajima
Rok vydání: 2019
Předmět:
Zdroj: Angewandte Chemie. 132:2282-2287
ISSN: 1521-3757
0044-8249
DOI: 10.1002/ange.201913533
Popis: By using a linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), nona- and hexadecanuclear copper hydride clusters, [Cu9 H7 (μ-dpmppm)3 ]X2 (X=Cl (1 a), Br (1 b), I (1 c), PF6 (1 d)) and [Cu16 H14 (μ-dpmppm)4 ]X2 (X2 =I2 (2 c), (4/3) PF6 ⋅(2/3) OH (2 d)) were synthesized and characterized. They form copper-hydride cages of apex-truncated supertetrahedral {Cu9 H7 }2+ and square-face-capped cuboctahedral {Cu16 H14 }2+ structures. The hydride positions were estimated by DFT calculations to be facially dispersed around the copper frameworks. A kinetically controlled synthesis gave an unsymmetrical Cu8 H6 cluster, [Cu8 H6 (μ-dpmppm)3 ]2+ (3), which readily reacted with CO2 to afford linear Cu4 complexes with formate bridges, leading to an unprecedented hydrogenation of CO2 into formate catalyzed by {Cu4 (μ-dpmppm)2 } platform. The results demonstrate that new motifs of copper hydride clusters could be established by the tetraphosphine ligands, and the structures influence their reactivity.
Databáze: OpenAIRE
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