Issue 3, 2011
From the journal:

Dalton Transactions

Unprecedented coordination of dithiocarbimate in multinuclear and heteroleptic complexes†

Bandana Singh,a   Michael G. B. Drew,‡b   Gabriele Kociok-Kohn,c   Kieran C. Molloy‡c  and  Nanhai Singh§*a  

* Corresponding authors

a Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, India
E-mail: nsingh@bhu.ac.in
Fax: +91 542 2368127
Tel: +91 542 2307321*108

b Department of Chemistry, University of Reading, Whiteknights, Reading, UK

c Department of Chemistry, University of Bath, Bath, UK

Abstract

An uncommon coordination protocol induced by the p-tolylsulfonyl dithiocarbimate ligand (L) [L = p-CH3C6H4SO2N[double bond, length as m-dash]CS22−] in conjunction with PPh3 allowed the formation of novel homodimetallic, Cu2(PPh3)4L (1), trinuclear heterometallic Cu2Ni(L)2(PPh3)4 (2) and heteroleptic complexes of general formula cis-[M(PPh3)2L] [M = Pd(II) (3), Pt(II) (4)]. The complexes have been characterized by microanalysis, mass spectrometry, IR, 1H, 13C and 31P NMR and electronic absorption spectra and single-crystal X-ray crystallography. 2 uniquely consists of square planar, trigonal planar and tetrahedral coordination spheres within the same molecule. In both heteroleptic complexes 3 and 4 the orientation of aromatic protons of PPh3 ligand towards the Pd(II) and Pt(II) center reveals C–H⋯Pd and C–H⋯Pt rare intramolecular anagostic or preagostic interactions. These complexes exhibit photoluminescent properties in solution at room temperature arising mainly from intraligand charge transfer (ILCT) transitions. The assignment of electronic absorption bands has been corroborated by time dependent density functional theory (TD-DFT) calculations. Complexes 1 and 2 with σrt values ∼ 10−6 S cm−1 show semi-conductor properties in the temperature range 313–403 K whereas 3 and 4 exhibit insulating behaviour.

Graphical abstract: Unprecedented coordination of dithiocarbimate in multinuclear and heteroleptic complexes

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Article information

DOI
https://doi.org/10.1039/C0DT00582G
Article type
Paper
Submitted
01 Jun 2010
Accepted
14 Oct 2010
First published
02 Dec 2010

Dalton Trans., 2011,40, 623-631

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Unprecedented coordination of dithiocarbimate in multinuclear and heteroleptic complexes

B. Singh, M. G. B. Drew, G. Kociok-Kohn, K. C. Molloy and N. Singh, Dalton Trans., 2011, 40, 623 DOI: 10.1039/C0DT00582G

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