Synthesis, spectroscopy, structure and photophysical properties of dinaphthylmethylarsine complexes of palladium(II) and platinum(II) Prasad P. Phadnis a , Vimal K. Jain a, * , Thilo Schurr b , Axel Klein b, * , Falk Lissner b , Thomas Schleid b , Wolfgang Kaim b a Novel Materials and Structural Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India b Institut fu ¨ r Anorganische Chemie, Universita ¨ t Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany Received 12 August 2004; accepted 6 March 2005 Available online 20 April 2005 Abstract Dinaphthylmethylarsine complexes of palladium(II) and platinum(II) with the formulae [MX 2 L 2 ] (M = Pd, Pt; L = di(1-naph- thyl)methylarsine = Nap 2 AsMe and X = Cl, Br, I), [M 2 Cl 2 (l-Cl) 2 L 2 ], [PdCl(S 2 CNEt 2 )L], [Pd 2 Cl 2 (l-OAc) 2 L 2 ] and [MCl 2 (PR 3 )L] (PR 3 = PEt 3 , PPr 3 , PBu 3 , PMePh 2 ) have been prepared. These complexes have been characterized by elemental analyses, IR, Raman, NMR ( 1 H, 13 C, 31 P) and UV–vis spectroscopy. The stereochemistry of the complexes has been deduced from the spectro- scopic data. The crystal structures of trans-[PdCl 2 (PEt 3 )(Nap 2 AsMe)] and of [Pd(S 2 CNEt 2 ) 2 ], a follow-up product, were determined. The UV–vis spectra of [MX 2 L 2 ] complexes show a red shift on going from X = Cl to X = I. The complexes [PdX 2 L 2 ] and [PtX 2 L 2 ] are strongly luminescent in fluid solution and in the solid at ambient temperature. Ó 2005 Elsevier B.V. All rights reserved. Keywords: Organoarsenic compounds; Palladium complexes; Platinum complexes; Crystal structures; Photoluminescence 1. Introduction During the last decade, the chemistry of organoarse- nic compounds has witnessed extensive growth due to the development of new ligands and due to the search for molecular precursors for CVD [1–4]. Arsines con- taining a 1-naphthyl group could be of interest because the facile cleavage of the M–C(naphthyl) linkage should render them as ideal components for molecular precur- sors. Besides, coordinated naphthylarsines in metal complexes may cause steric crowding, thus facilitating, e.g., the ortho metallation of the aromatic carbon atom [5,6]. In view of this and in pursuance of our work on organoarsines, we have now examined the chemistry of di(1-naphthyl)methylarsine (Nap 2 AsMe = L) with palla- dium(II) and platinum(II). 2. Experimental 2.1. General procedures The compounds Na 2 PdCl 4 , [PdCl 2 (MeCN) 2 ] and [PtCl 2 (PhCN) 2 ] were prepared according to the litera- ture procedures [7]. All reactions were carried out under a nitrogen atmosphere in dry and distilled analytical grade solvents. Microanalyses were carried out in the Analytical Chemistry Division, BARC. The 1 H, 13 C{ 1 H} and 31 P{ 1 H}NMR spectra were recorded on a Bruker DPX-300 spectrometer operating at 300, 75.47 and 121.49 MHz, respectively. Chemical shifts are relative to internal chloroform peak [d = 7.26 ppm 0020-1693/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2005.03.026 * Corresponding authors. Present address: Institute for Inorganic Chemistry, University of Cologne, Greinstrasse 6, D-50939 Cologne, Germany. Tel.: +49 221 470 4006; fax: +49 221 470 4899. E-mail addresses: jainvk@apsara.barc.ernet.in (V.K. Jain), aklein @iac.uni-stuttgart.de, axel.klein@uni-koeln.de (A. Klein). www.elsevier.com/locate/ica Inorganica Chimica Acta 358 (2005) 2609–2617