Premium
5,6‐ and 6,6‐Membered Palladium(II) Pincer Complexes Based on Functionalized Carboxamides with Ancillary Sulfur and Nitrogen Donors
Author(s) -
Churusova Svetlana G.,
Aleksanyan Diana V.,
Vasil'ev Andrei A.,
Nelyubina Yulia V.,
Novikov Valentin V.,
Pavlov Alexander A.,
Denisov Gleb L.,
Klemenkova Zinaida S.,
Kozlov Vladimir A.
Publication year - 2016
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.201601093
Subject(s) - chemistry , pincer movement , denticity , palladium , aryl , ligand (biochemistry) , sulfur , sulfoxide , sulfide , pincer ligand , medicinal chemistry , chloride , derivative (finance) , polymer chemistry , combinatorial chemistry , organic chemistry , catalysis , crystal structure , alkyl , financial economics , economics , biochemistry , receptor
New multidentate ligands have been synthesized by the condensation of 2‐(methylsulfanyl)benzoyl chloride with a range of amines bearing ancillary N or S donors. In reactions with PdCl 2 (NCPh) 2 , the ligands smoothly underwent direct cyclopalladation to give pincer complexes with 5,6‐ or 6,6‐membered fused metallocycles. The oxidation of the sulfide ligands with H 2 O 2 afforded the corresponding sulfoxide derivatives, which readily formed analogous pincer complexes with the Pd II ions. The realization of κ 3 ‐ S , N , X coordination (X = N or S) was confirmed by multinuclear NMR and IR spectroscopic data and, in some cases, X‐ray crystallography. An unusual dynamic behavior of the 6,6‐membered S , N , S complex with an organophosphorus ligand was additionally studied by the ROESY technique. All of the palladocycles obtained were tested as precatalysts for the Suzuki cross‐coupling of aryl bromides with arylboronic acids, which allowed us to evaluate the main structure–activity relationships.