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Palladium(II) and platinum(II) 2-(methoxycarbonyl)ethylselenolates:Synthesis, spectroscopy, structures and their conversion into metal selenide

Kumbhare, Liladhar B and Jain, Vimal K and Phadnis, Prasad P and Nethaji, Munirathinam (2007) Palladium(II) and platinum(II) 2-(methoxycarbonyl)ethylselenolates:Synthesis, spectroscopy, structures and their conversion into metal selenide. In: Journal of Organometallic Chemistry, 692 (7). pp. 1546-1556.

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Abstract

A diselenide, $(MeOOCCH_2CH_2Se)_2$ (1) has been prepared by esterification of $(HOOCCH_2CH_2Se)_2$ in methanol. The reductive cleavage of Se–Se bond in 1 by $NaBH_4$ in methanol generates $MeOOCCH_2CH_2SeNa$. The latter in different stoichiometries reacts with $[M_2Cl_2(\mu-Cl)_2(PR_3)_2]$ to give a variety of products of compositions $[M_2Cl_2(\mu-SeCH_2CH_2COOMe)_2(PR_3)_2]$ (2); $[M_2Cl_2(\mu-Cl)-(\mu-SeCH_2CH_2COOMe)(PR_3)_2]$ (3); $[Pd_2 SeCH_2CH_2COOMe)_2(\mu-SeCH_2CH_2COOMe)_2(PR_3)_2]$ (4); $[Pd_3Cl_2(\mu-SeCH_2CH_2COOMe)_4(PR_3)_2]$ (5). Treatment of complexes 2 with $[M_2Cl_2(\mu-Cl)_2(PR_3)_2]$ affords complexes 3 in nearly quantitative yield. The formation of various products in these reactions is sensitive to stoichiometric ratio of reactants employed. This enables interconversion of various complexes by manipulating mole ratios of appropriate starting materials. A homoleptic palladium complex, $[Pd(SeCH_2CH_2COOMe)_2]_6$ (6) was isolated from a reaction between $Na_2PdCl_4$ and $MeOOCCH_2CH_2SeNa$. All these complexes have been characterized by elemental analysis, IR, UV–Vis and NMR $(^1H, ^{13}C, ^{31}P, ^{77}Se, ^{195}Pt)$ spectroscopy. Structures of trans-$[Pd _2Cl_2(\mu-SeCH_2CH_2COOMe)_2(PPh_3)_2]$ (2d), $[Pt_2Cl_2(\mu-Cl)(\mu-SeCH_2CH_2COOMe)(P^nPr_3)_2] (3e), [Pd_3Cl_2(\mu-SeCH_2CH_2COOMe)_4(P^nPr_3)_2]$ (5) and $[Pd(SeCH_2CH_2COOMe)_2]_6$ (6) have been established unambiguously by X-ray crystallography. In these complexes, there are bridging selenolate ligands with their uncoordinated ester groups. Compound 6 has a centrosymmetric $Pd_6Se_{12}$ hexagon in which every two palladium atoms are bridged by selenolate ligands. Thermal behaviour of some complexes has been investigated. Pyrolysis of compound 2b in tributylphosphate at 195 $^oC$ gave $Pd_{17}Se_{15}$ nanoparticles which were characterized by XRD and EDAX.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier.
Keywords: Palladium;Platinum;Selenolates;NMR;Palladium selenide;X-ray
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 14 Aug 2007
Last Modified: 19 Sep 2010 04:39
URI: http://eprints.iisc.ernet.in/id/eprint/11711

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