Premium
Pd II and Pt II Complexes of 2‐(2′‐Pyridyl)‐4,6‐diphenylphosphinine: Synthesis, Structure, and Reactivity
Author(s) -
CamposCarrasco Ariadna,
Broeckx Leen E. E.,
Weemers Jarno J. M.,
Pidko Evgeny A.,
Lutz Martin,
MasdeuBultó Anna M.,
Vogt Dieter,
Müller Christian
Publication year - 2011
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.201002586
Subject(s) - chemistry , denticity , reactivity (psychology) , ligand (biochemistry) , chelation , palladium , crystallography , methanol , medicinal chemistry , double bond , crystal structure , x ray crystallography , stereochemistry , catalysis , diffraction , inorganic chemistry , polymer chemistry , organic chemistry , receptor , medicine , pathology , physics , optics , biochemistry , alternative medicine
The coordination chemistry of the bidentate P,N hybrid ligand 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine ( 1 ) towards Pd II and Pt II has been investigated. The molecular structures of the complexes [PdCl 2 ( 1 )] and [PtCl 2 ( 1 )] were determined by X‐ray diffraction, representing the first crystallographically characterized λ 3 ‐phosphinine–Pd II and –Pt II complexes. Both complexes reacted with methanol at the P=C double bond at an elevated temperature, leading to the corresponding products [MCl 2 ( 1 H⋅OCH 3 )]. The molecular structure of [PdCl 2 ( 1 H⋅OCH 3 )] was determined crystallographically and revealed that the reaction with methanol proceeds selectively by syn addition and exclusively to one of the P=C double bonds. Strikingly, the reaction of [PdCl 2 ( 1 H⋅OCH 3 )] with the chelating diphosphine DPEphos at room temperature in CH 2 Cl 2 led quantitatively to [PdCl 2 (DPEphos)] and phosphinine 1 by elimination of CH 3 OH and rearomatization of the phosphorus heterocycle.