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The Coordination Chemistry of Pentafluorophenylphosphino Pincer Ligands to Platinum and Palladium
Author(s) -
Anderson Bradley G.,
Spencer John L.
Publication year - 2014
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.201304398
Subject(s) - pincer movement , chemistry , palladium , ligand (biochemistry) , platinum , medicinal chemistry , decarbonylation , pincer ligand , coordination complex , stereochemistry , carbon monoxide , metal , catalysis , organic chemistry , biochemistry , receptor
Abstract The synthesis of electron‐poor PCP pincer ligands 1,3‐((C 6 F 5 ) 2 PO) 2 C 6 H 4 , 1,3‐((C 6 F 5 ) 2 PCH 2 ) 2 C 6 H 4 , and 1‐((C 6 F 5 ) 2 PO)‐3‐( t Bu 2 PCH 2 )C 6 H 4 , and their coordination chemistry to platinum and palladium is described. The most electron‐poor ligand 1,3‐((C 6 F 5 ) 2 PO) 2 C 6 H 4 (POCOPH) reacts with Group 10 metal chloride precursors to form a range of unusual cis , trans ‐dimers of the type κ 2 ‐P,P‐[(POCOPH)MCl(L)] 2 (M=Pt, Pd; L=Cl, Me), which undergo metallation to form [(POCOP)MCl] pincer complexes only under prolonged thermolysis. The formation of such cis , trans ‐dimers during pincer complex formation can be mitigated through the use of starting materials with more strongly binding ancillary ligands, improving the overall rate of ligand metallation. Carbonyl complexes of the type [(PCP)M(CO)] + were synthesised from the pincer chloride complexes by halide abstraction, and displayed large ν (CO) values, from 2170–2111 cm −1 , confirming the electron‐poor nature of the compounds. The [(PCP)Pd(CO)] + complexes also demonstrated the ability to reversibly bind carbon monoxide both in solution and the solid state, with the rate of decarbonylation increasing with increasing wavenumber for the CO stretch.