Facially Dispersed Polyhydride Cu9 and Cu16 Clusters Comprising Apex-Truncated Supertetrahedral and Square-Face-Capped Cuboctahedral Copper Frameworks.
Angew Chem Int Ed Engl
; 59(6): 2262-2267, 2020 Feb 03.
Article
em En
| MEDLINE
| ID: mdl-31724276
ABSTRACT
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 â
(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.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2020
Tipo de documento:
Article
País de afiliação:
Japão