Mixed phosphine/diimines and/or amines ruthenium carbonyl complexes: Synthesis, characterization and transfer-hydrogenation

被引：19
作者：
Cavarzan, Deividi A. [1 ]
Fagundes, Francisco D. [1 ]
Fuganti, Otavio [1 ]
da Silva, Caroline W. P. [1 ]
Pinheiro, Carlos Basilio [2 ]
Back, Davi F. [3 ]
Barison, Andersson [1 ]
Bogado, Andre L. [4 ]
de Araujo, Marcio P. [1 ]
机构：
[1] Univ Fed Parana, Dept Quim, Ctr Politecn, CP 19081, BR-81531980 Curitiba, Parana, Brazil
[2] Univ Fed Minas Gerais, Dept Fis, ICEX, BR-31270901 Belo Horizonte, MG, Brazil
[3] Univ Fed Santa Maria, Dept Quim, BR-97105900 Santa Maria, RS, Brazil
[4] Univ Fed Uberlandia, Fac Ciencias Integradas Pontal, BR-38302000 Ituiutaba, MG, Brazil
来源：
POLYHEDRON | 2013年 / 62卷
关键词：
ASYMMETRIC HYDROGENATION; STEREOSELECTIVE HYDROGENATION; PYRIDINE-DERIVATIVES; DIHYDRIDE COMPLEXES; CATALYTIC-ACTIVITY; CRYSTAL-STRUCTURE; NMR-SPECTROSCOPY; KETONES; METATHESIS; REACTIVITY;
D O I：
10.1016/j.poly.2013.06.022
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
We synthesized complexes with the general formula trans-[RuCl2(CO)(PR3)(N-N)] (N-N = diimines and/or amines; PR3 = triphenylphosphine or tri-p-tolylphosphine) by reacting trans-[RuCl2(CO)(dmf)(PR3)(2)] (dmf = N,N-dimethylformamide) and the appropriate N-N donor ligands. We characterized the complexes by NMR (P-31, H-1, nOe, HMBC, and HSQC), FTIR, and elemental analyses; we also analyzed trans-[RuCl2(CO)(PPh3)(bipy)], trans, trans-[RuCl2(CO)(P{p-tol(3)})(ampy)] and trans, trans-[RuCl2(CO) (PPh3)(ampy)] by X-ray diffraction. We tested the complexes as pre-catalyst for the reduction of acetophenone in transfer-hydrogenation conditions, using isopropanol as the hydrogen source. The catalyst/base/substrate molar proportion of 1:20:1000 yielded conversions up to 83% in 24 h, whereas the proportion 1:20:500 furnished conversions up to 96% in 4 h. In addition, p-substituted acetophenone were reduced with conversions up to 95% within 135 min of reaction time. The complexes containing the ligands ampy and en were the most active-the "RuH-NH" unit promoted reactions via the outer-sphere mechanism. (c) 2013 Elsevier Ltd. All rights reserved.
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页码：75 / 82
页数：8
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