A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2

被引：44

作者：

Nakamae, Kanako ^{[1
]}

Tanaka, Miho ^{[1
]}

Kure, Bunsho ^{[1
]}

Nakajima, Takayuki ^{[1
]}

Ura, Yasuyuki ^{[1
]}

Tanase, Tomoaki ^{[1
]}

机构：

[1] Nara Womens Univ, Dept Chem, Fac Sci, Kitauoya Nishi Machi, Nara 6308506, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 40期

关键词：

carbon dioxide; copper; diphosphine; hydrides; multinuclear complex; CARBON-DIOXIDE; TETRAPHOSPHINE LIGANDS; NEUTRON-DIFFRACTION; CRYSTAL-STRUCTURE; COPPER HYDRIDES; COMPLEXES; NANOCLUSTER; CHAINS; HYDROSILYLATION; REDUCTION;

D O I：

10.1002/chem.201702071

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A copper hydride cluster [Cu-8(m-H)(6)(mu-dppm) (5)](PF6)(2) (dppm= bis(diphenylphosphino) methane) was prepared from reaction of [CuH(PPh3)](6) with dppm in the presence of [Cu(CH3CN)(4)] PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans-bicapped octahedral Cu-8 framework. The Cu8H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu-3(m-H)(m-O2CH)(m-dppm)(3)] PF6, which could be developed to unprecedented hydrosilylation of CO2 catalyzed by multinuclear CuH species under mild conditions.

引用

页码：9457 / 9461

页数：5

共 52 条

[1] LEWIS-BASE ADDUCTS OF GROUP-11 METAL(I) COMPOUNDS .49. STRUCTURAL CHARACTERIZATION OF HEXAMERIC AND PENTAMERIC (TRIPHENYLPHOSPHINE)COPPER(I) HYDRIDES [J].

ALBERT, CF ;

HEALY, PC ;

KILDEA, JD ;

RASTON, CL ;

SKELTON, BW ;

WHITE, AH .

INORGANIC CHEMISTRY, 1989, 28 (07) :1300-1306

[2]

[Anonymous], 2015, ANGEW CHEM, V127, P1030

[3]

[Anonymous], 2009, ANGEW CHEM, V121, P2191

[4]

[Anonymous], 2014, ANGEW CHEM, V126, P7342

[5]

[Anonymous], 2013, ANGEW CHEM, V125, P13158

[6] HYDROCONDENSATION OF CO2 .2. REACTION OF CARBON-DIOXIDE AND CARBON-MONOXIDE WITH [HCUPPH3]6 [J].

BEGUIN, B ;

DENISE, B ;

SNEEDEN, RPA .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1981, 208 (01) :C18-C20

[7] SYNTHESIS AND MOLECULAR GEOMETRY OF HEXAMERIC TRIPHENYLPHOSPHINOCOPPER(I) HYDRIDE AND CRYSTAL-STRUCTURE OF H6CU6(PPH3)6.HCONME2 [J].

CHURCHILL, MR ;

BEZMAN, SA ;

OSBORN, JA ;

WORMALD, J .

INORGANIC CHEMISTRY, 1972, 11 (08) :1818-+

[8] CHEMOENZYMATIC PREPARATION OF TRANS-2,6-DIALKYLPIPERIDINES AND OF OTHER AZACYCLE BUILDING-BLOCKS - TOTAL SYNTHESIS OF (+)-DESOXOPROSOPININE [J].

CIUFOLINI, MA ;

HERMANN, CW ;

WHITMIRE, KH ;

BYRNE, NE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (09) :3473-3475

[9] Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag6H4(dppm)4(OAc)2] and [Cu3H(dppm)3(OAc)2] [J].

Cook, Andrew W. ;

Nguyen, Thuy-Ai D. ;

Buratto, William R. ;

Wu, Guang ;

Hayton, Trevor W. .

INORGANIC CHEMISTRY, 2016, 55 (23) :12435-12440

[10] CuH-catalyzed reactions [J].

Deutsch, Carl ;

Krause, Norbert ;

Lipshutz, Bruce H. .

CHEMICAL REVIEWS, 2008, 108 (08) :2916-2927

← 1 2 3 4 5 6 →