反式-二甲基膦乙烷合钼（H）（NO）与亚胺的插入反应。

Insertion reactions of trans-Mo(dmpe)2(H)(NO) with imines.

作者信息

Liang Fupei, Schmalle Helmut W, Berke Heinz

机构信息

Anorganisch-Chemisches Institut der Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland.

出版信息

Inorg Chem. 2004 Feb 9;43(3):993-9. doi: 10.1021/ic030139l.

DOI:10.1021/ic030139l

PMID:14753821

Abstract

The insertion chemistry of the hydride complex trans-Mo(dmpe)(2)(H)(NO) (1) (dmpe = bis(dimethylphosphino)ethane) with imines has been investigated. It was found that disubstituted aromatic imines RCH[double bond]NR' (R, R' = Ar) insert into the Mo-H bond of 1, while a series of various mono- and other disubstituted imines do not react. The insertion products trans-Mo(dmpe)(2)(NO)[NR'(CH(2)R)] (R = R' = Ph (2); R = Cp(2)Fe, R' = Ph (3); R = Ph, R' = Cp(2)Fe (4); R = 1-naphthyl, R' = Ph (5)) have been isolated and fully characterized by elemental analysis, IR and NMR spectroscopy, and mass spectrometry. The imine PhCH[double bond]NC(10)H(7) (C(10)H(7) = 1-naphthyl) reacted with 1 establishing an equilibrium to produce the nonisolable complex trans-Mo(dmpe)(2)(NO)[NC(10)H(7)(CH(2)Ph)] (6). The equilibrium constant for this reaction has been derived from VT-NMR measurements, and the Delta H and Delta S values of this reaction were calculated to be -48.8 +/- 0.4 kJ.mol(-1) and -33 +/- 1 J.K(-1).mol(-1) reflecting a mild exothermic process and its associative nature. Single-crystal X-ray diffraction analyses were carried out on 2-5.

摘要

研究了氢化物配合物反式-Mo(dmpe)₂(H)(NO) (1)（dmpe = 双(二甲基膦基)乙烷）与亚胺的插入化学。发现二取代芳基亚胺RCH=NR'（R、R' = 芳基）插入到1的Mo-H键中，而一系列各种单取代和其他二取代亚胺不发生反应。已分离出插入产物反式-Mo(dmpe)₂(NO)[NR'(CH₂R)]（R = R' = Ph (2)；R = Cp₂Fe，R' = Ph (3)；R = Ph，R' = Cp₂Fe (4)；R = 1-萘基，R' = Ph (5)），并通过元素分析、红外光谱和核磁共振光谱以及质谱对其进行了全面表征。亚胺PhCH=NC₁₀H₇（C₁₀H₇ = 1-萘基）与1反应建立平衡，生成不可分离的配合物反式-Mo(dmpe)₂(NO)[NC₁₀H₇(CH₂Ph)] (6)。该反应的平衡常数已通过变温核磁共振测量得出，该反应的ΔH和ΔS值经计算分别为-48.8±0.4 kJ·mol⁻¹和-33±1 J·K⁻¹·mol⁻¹，反映出温和的放热过程及其缔合性质。对2 - 5进行了单晶X射线衍射分析。