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Synthesis and Characterization of Stable Gold(III) PNP Pincer Complexes
Author(s) -
Grajeda Javier,
Nova Ainara,
Balcells David,
Bruch Quinton J.,
Wragg David S.,
Heyn Richard H.,
Miller Alexander J. M.,
Tilset Mats
Publication year - 2018
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.201800019
Subject(s) - chemistry , pincer movement , reactivity (psychology) , alkene , amide , ligand (biochemistry) , pincer ligand , medicinal chemistry , ethylene , nuclear magnetic resonance spectroscopy , crystallography , stereochemistry , catalysis , organic chemistry , medicine , alternative medicine , receptor , pathology , biochemistry
The first mononuclear Au III PNP pincer complexes [PNP = bis(2‐diisopropylphosphinophenyl)amide] are reported. The chloro complex [(PNP)Au(Cl)][OAc F ] (OAc F = OCOCF 3 ) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PN H P ligand. Dehalogenation with AgOAc F afforded the trifluoroacetate‐bound complex [(PNP)Au(OAc F )][OAc F ]. Both complexes were characterized by NMR spectroscopy and X‐ray crystallography. Electronic absorption spectroscopy and TD‐DFT studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au III trifluoroacetate complex is surprisingly stable, and no alkene insertion was observed under ethylene (C 2 H 4 ), even under high pressures and at high temperatures. DFT calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic C 2 H 4 ‐bound intermediate invoked in a formal insertion reaction.