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π‐Accepting‐Pincer Rhodium Complexes: An Unusual Coordination Mode of PCP‐Type Systems
Author(s) -
Kossoy Elizaveta,
Iron Mark A.,
Rybtchinski Boris,
BenDavid Yehoshoa,
Shimon Linda J. W.,
Konstantinovski Leonid,
Martin Jan M. L.,
Milstein David
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401116
Subject(s) - rhodium , pincer movement , phosphine , pincer ligand , ligand (biochemistry) , chemistry , coordination complex , density functional theory , stereochemistry , crystallography , catalysis , computational chemistry , organic chemistry , receptor , metal , biochemistry
Abstract The novel π‐accepting, pincer‐type ligand, d i py rrolyl p hoshino x ylene (DPyPX), is introduced. This ligand has the strongest π‐accepting phosphines used so far in the PCP family of ligands and this results in some unusual coordination chemistry. The rhodium( I ) complex, [(DPyPX)Rh(CO)(PR 3 )] ( 4 , R=Ph, Et, pyrrolyl) is prepared by treating the relevant [(DPyPX)Rh(PR 3 )] ( 3 ) complex with CO and is remarkably resistant to loss of either ligand. X‐ray crystallographic analysis of complex 4 b (R=Et) reveals an unusual cisoid coordination of the PCP phosphine ligands. These observations are supported by density functional theory (DFT) calculations.