用于醇氧化反应的高度协同的四金属钌-μ-氧-μ-羟基催化剂。
Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction.
作者信息
Yi Chae S, Zeczycki Tonya N, Guzei Ilia A
机构信息
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881, and Molecular Structure Laboratory, Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706-1396.
出版信息
Organometallics. 2006;25(4):1047-1051. doi: 10.1021/om0510674.
Abstract
The tetrametallic ruthenium-oxo-hydroxo-hydride complex {(PCy(3))(CO)RuH(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.
摘要
四金属钌-氧-氢氧根-氢配合物{(PCy(3))(CO)RuH(μ(4)-O)(μ(3)-OH)(μ(2)-OH)} (1)由单体配合物(PCy(3))(CO)RuHCl (2)分两步合成。发现四聚体配合物1是醇转移脱氢的高效催化剂。如对p-X-C(6)H(4)CH(2)OH (ρ = -0.45)和p-X-C(6)H(4)CH(OH)CH(3) (ρ = +0.22) (X = OMe、CH(3)、H、Cl、CF(3))氧化反应的哈米特相关性所示，配合物1对伯苄醇和仲苄醇表现出不同的催化活性模式。初始速率对[PhCH(OH)CH(3)]作图得到的S形曲线(K(0.5) = 0.34 M；希尔系数，n = 4.2±0.1)以及膦抑制动力学均表明该配合物对仲醇氧化具有高度协同性。
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本文引用的文献
1
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Angew Chem Int Ed Engl. 1998 Aug 17;37(15):2096-2099. doi: 10.1002/(SICI)1521-3773(19980817)37:15<2096::AID-ANIE2096>3.0.CO;2-B.
2
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Acc Chem Res. 1996 Jul;29(7):348-54. doi: 10.1021/ar950150s.
3
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J Am Chem Soc. 2005 Oct 12;127(40):14062-71. doi: 10.1021/ja053956o.
4
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5
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J Org Chem. 2005 Apr 15;70(8):3140-7. doi: 10.1021/jo047737h.
6
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7
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8
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