Comparative theoretical study of [3+2] and [2+2] cycloadditions of ethylene and WXYMe2; X, Y = (=O), (=NH), (=CH2)

被引：8

作者：

Haunschild, Robin ^{[2
]}

Frenking, Gernot ^{[1
]}

机构：

[1] Univ Marburg, Fachbereich Chem, D-35043 Marburg, Germany

[2] Rice Univ, Dept Chem, Houston, TX 77005 USA

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2009年 / 694卷 / 25期

关键词：

Metal oxo amido carbene complexes; Reaction mechanism; DFT calculations; Cycloadditions; OSMIUM-CATALYZED DIHYDROXYLATION; GAUSSIAN-BASIS SETS; OXO COMPLEXES; METAL-OXIDES; OLEFINS;

D O I：

10.1016/j.jorganchem.2009.08.022

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Quantum chemical calculations employing density functional theory (B3LYP) were carried out to compare the preference of [3+2] versus [2+2] cycloadditions of ethylene to WO2(CH3)(2) (W2), WONH(CH3)(2) (W3), WNHCH2(CH3)(2) (W4), W(CH2)(2)(CH3)(2) (W5), and W(NH)(2)(CH3)(2) (W6). The results are compared to previously published data on the related tungsten complex WOCH2(CH3)(2) (W1). In agreement with MoOCH2(CH3)(2) and ReO2CH3CH2, all six tungsten complexes prefer a [2+2] pathway rather than a [3+2] cycloaddition which is the reverted preference compared to the analogous compounds TcO2CH3CH2, MnO2CH3CH2, RuO3CH2, OsO3CH2 and OsO2(NH)(2), and MO2CH3CH2 (M = Ir, Rh, Co). (C) 2009 Elsevier B. V. All rights reserved.

引用

页码：4090 / 4093

页数：4

共 33 条

[1] ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].