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Facially Dispersed Polyhydride Cu 9 and Cu 16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks
Author(s) -
Nakamae Kanako,
Nakajima Takayuki,
Ura Yasuyuki,
Kitagawa Yasutaka,
Tanase Tomoaki
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201913533
Subject(s) - copper , hydride , formate , chemistry , cluster (spacecraft) , crystallography , reactivity (psychology) , catalysis , metal , organic chemistry , medicine , alternative medicine , pathology , computer science , programming language
By using a linear tetraphosphine, meso ‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), nona‐ and hexadecanuclear copper hydride clusters, [Cu 9 H 7 (μ‐dpmppm) 3 ]X 2 (X=Cl ( 1 a ), Br ( 1 b ), I ( 1 c ), PF 6 ( 1 d )) and [Cu 16 H 14 (μ‐dpmppm) 4 ]X 2 (X 2 =I 2 ( 2 c ), (4/3) PF 6 ⋅(2/3) OH ( 2 d )) were synthesized and characterized. They form copper‐hydride cages of apex‐truncated supertetrahedral {Cu 9 H 7 } 2+ and square‐face‐capped cuboctahedral {Cu 16 H 14 } 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 Cu 8 H 6 cluster, [Cu 8 H 6 (μ‐dpmppm) 3 ] 2+ ( 3 ), which readily reacted with CO 2 to afford linear Cu 4 complexes with formate bridges, leading to an unprecedented hydrogenation of CO 2 into formate catalyzed by {Cu 4 (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.