π-Accepting-Pincer Rhodium Complexes: An Unusual Coordination Mode of PCP-Type Systems
✍ Scribed by Elizaveta Kossoy; Mark A. Iron; Boris Rybtchinski; Yehoshoa Ben-David; Linda J. W. Shimon; Leonid Konstantinovski; Jan M. L. Martin; David Milstein
- Publisher
- John Wiley and Sons
- Year
- 2005
- Tongue
- English
- Weight
- 209 KB
- Volume
- 11
- Category
- Article
- ISSN
- 0947-6539
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✦ Synopsis
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.