TY - JOUR
T1 - Comparative theoretical study of [3+2] and [2+2] cycloadditions of ethylene and WXYMe2; X, Y = ({double bond, long}O), ({double bond, long}NH), ({double bond, long}CH2)
AU - Haunschild, Robin
AU - Frenking, Gernot
PY - 2009/12/1
Y1 - 2009/12/1
N2 - 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).
AB - 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).
KW - Cycloadditions
KW - DFT calculations
KW - Metal oxo amido carbene complexes
KW - Reaction mechanism
UR - http://www.scopus.com/inward/record.url?scp=70350100317&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2009.08.022
DO - 10.1016/j.jorganchem.2009.08.022
M3 - 文章
AN - SCOPUS:70350100317
SN - 0022-328X
VL - 694
SP - 4090
EP - 4093
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 25
ER -