Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I)

Ahuja, Ritu and Nethaji, Munirathinam and Samuelson, Ashoka G (2011) Chelating and bridging bis(diphenylphosphino)aniline complexes of copper(I). In: Inorganica Chimica Acta, 372 (1, Sp.). pp. 220-226.

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Abstract

The ligand bis(diphenylphosphino)aniline (dppan) has been shown to be a versatile ligand sporting different coordination modes and geometries as dictated by copper(I) and the counter ion. The molecular structures of its Cu(I) complexes were characterized by X-ray crystallography. The ligand was found in a chelating mode and monomeric complexes were formed when the ligand to copper ratio was 2: 1 and the anion was non-coordinating. However, with thiocyanate as the counter anion, the ligand was found to adopt two different modes, with one ligand chelating and the other acting as a monodentate ligand. With CuX (X = Cl, Br), dppan formed a tetrameric complex when the ligand and metal were reacted in the ratio of 1:1. But reactions containing ligand and metal in the ratios of 1: 2 or 2: 1, resulted in the formation of a mixture of species in solution. Crystallization however, led to the isolation of the tetrameric complex. Variable temperature P-31{H-1} NMR spectra of the isolated tetramers did not show the presence of chelated structures in solution. Tetra-alkylammonium salts were added to solutions of various complexes of dppan and studied by P-31{H-1} NMR to probe the effect of anions on the stability of complexes in solution. The Cu-dppan complexes were robust and did not interconvert with other structures in solution unlike the bis(diphenylphosphino) isopropylamine complexes. (C) 2011 Elsevier B.V. All rights reserved.

Item Type:	Journal Article
Publication:	Inorganica Chimica Acta
Publisher:	Elsevier Science
Additional Information:	Copyright of this article belongs to Elsevier Science.
Keywords:	Binding mode;Copper(I);Diphosphinoamine;Nuclearity;Short bite ligands
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	15 Jun 2011 05:52
Last Modified:	15 Jun 2011 05:52
URI:	http://eprints.iisc.ac.in/id/eprint/38251

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