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Synthesis, Characterization, and Reactivity of Neutral and Cationic Pd–C,N,N Pincer Complexes
Author(s) -
Bianchini Claudio,
Lenoble Géraldine,
Oberhauser Werner,
Parisel Sébastien,
Zanobini Fabrizio
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500479
Subject(s) - chemistry , pincer movement , cationic polymerization , palladium , phenylboronic acid , reactivity (psychology) , medicinal chemistry , pyridine , pincer ligand , benzene , ligand (biochemistry) , crystal structure , catalysis , nuclear magnetic resonance spectroscopy , stereochemistry , crystallography , polymer chemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
The ortho ‐palladation of the iminophosphane ligand 6‐phenyl‐2‐[(2,6‐diisopropylphenyl)imino]pyridine ( HL ) with Pd(OAc) 2 and PdCl 2 (PhCN) 2 in benzene yields the neutral Pd–C,N,N pincer complexes Pd(OAc)(κ 3 ‐C,N,N‐L) ( 1 ) and PdCl(κ 3 ‐C,N,N‐L) ( 2 ), respectively. In the presence of NaBAr′ 4 [Ar′ = 3,5‐(CF 3 ) 2 C 6 H 3 ], 2 reacts in CH 2 Cl 2 with MeCN, PPh 3 , or PH[ o ‐MeO(C 6 H 4 )] 2 to give the cationic palladium( II ) pincer complexes [Pd(CH 3 CN)(κ 3 ‐C,N,N‐L)]BAr′ 4 ( 3 ), [Pd(PPh 3 )(κ 3 ‐C,N,N‐L)]BAr′ 4 ( 4 ) and {Pd[PH( o ‐MeOC 6 H 4 ) 2 ](κ 3 ‐C,N,N‐L)}BAr′ 4 ( 5 ), respectively. Complexes 1 – 5 have been characterized by multinuclear NMR and IR spectroscopy. The solid‐state structures of 1 and 2 have been determined by single‐crystal X‐ray diffraction techniques. Both the neutral compounds 1 and 2 and the cationic derivatives 3 , 4 , and 5 were tested as catalyst precursors for the Suzuki cross‐coupling of 4‐bromo‐ and 4‐chloroacetophenone with phenylboronic acid. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)