Terminal Imido Rhodium Complexes

被引：30
作者：
Geer, Ana M. [1 ]
Tejel, Cristina [1 ]
Lopez, Jose A. [1 ]
Ciriano, Miguel A. [1 ]
机构：
[1] Univ Zaragoza, CSIC, ISQCH, Dept Quim Inorgan, E-50009 Zaragoza, Spain
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 22期
基金：
奥地利科学基金会;
关键词：
azides; cycloaddition; multiple bonds; rhodium; structure elucidation; H BOND AMINATION; CATALYZED OLEFIN AZIRIDINATION; NITRENE COMPLEXES; COBALT(III) IMIDO; SPIN-CROSSOVER; REACTIVITY; LIGANDS; NICKEL; IRON; MECHANISM;
D O I：
10.1002/anie.201400023
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Compounds of the late transition metals with M=X multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second-and third-row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity studies of the first rhodium complexes [Rh(PhBP3)(NR)] (PhBP3=PhB{CH2PPh2}(3)) with a multiple and terminal Rh=N bond. These imido compounds result from reactions of organic azides with the corresponding rhodium(I) complex having a labile ligand, and display a pseudo-tetrahedral core geometry with an almost linear Rh-N-C arrangement [177.5(2)degrees] and a short Rh-N bond [1.780(2) angstrom]. We also show that the Rh=N bond undergoes protonation at the nitrogen atom or addition of H-2, and also engages in nitrene-group transfer and cycloaddition reactions.
引用
收藏
页码：5614 / 5618
页数：5
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