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Chalcogenolato-bridged cyclometallated binuclear palladium complexes: Synthesis, spectroscopy, structures of ${[Pd_2(\mu-Cl)(\mu-SMes)(C_{10}H_6NMe_2–C,N)_2]}$ and ${[Pd_2(\mu-SePh)_2(C_{10}H_6NMe_2–C,N)_2]}$

Ghavale, Ninad D and Dey, Sandip and Jain, Vimal K and Nethaji, M (2008) Chalcogenolato-bridged cyclometallated binuclear palladium complexes: Synthesis, spectroscopy, structures of ${[Pd_2(\mu-Cl)(\mu-SMes)(C_{10}H_6NMe_2–C,N)_2]}$ and ${[Pd_2(\mu-SePh)_2(C_{10}H_6NMe_2–C,N)_2]}$. In: Inorganica Chimica Acta, 361 (8). pp. 2462-2470.

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Abstract

Reactions of orthometallated binuclear palladium complexes with NaER, obtained by {NaBH_4} reduction of {R_2E_2} in methanol, gave complexes, ${[Pd_2(\mu-ER)_2(C^\capY)_2]}$ ${(HC^\capY)}$ = N,N-dimethylbenzylamine {(C_6H_5CH_2NMe_2)}, N,N-dimethylnaphthylamine {(C_10H_7NMe_2)}, tri-o-tolylphosphine ${P(tol-o)_3}$; ER=SePh, SeMes, TePh, TeMes $(Mes = 2,4,6-Me_3C_6H_2)$. Similar reactions of ${[Pd_2(\mu-Cl)_2} (C_10H_6NMe_2–C,N)_2]}$ with ${Pb(SMes)_2}$ or MesSH in the presence of {NaHCO_3} gave chloro/thiolato-bridged complex ${[Pd_2(\mu-Cl)(\mu-SMes)(C_10H_6NMe_2–C,N)_2]}$. The newly synthesized complexes were characterized by elemental analysis, UV–Vis, IR, NMR {(^1H, ^{13}C, ^{31}P, ^{77}Se, ^{125}Te)} spectroscopy. These complexes crystallized out preferentially in sym-cis configuration. A low energy charge transfer transition has been identified from chalcogenolate centers to an emptyπ* orbital of cyclometallated ligand in absorption spectroscopy in these complexes. The structures of ${[Pd_2(\mu-Cl)(\mu-SMes)(C_10H_6NMe_2–C,N)_2]}$ (1) and ${[Pd_2(\mu-SePh)_2(C-10H_6NMe_2–C,N)_2]}$ (3) have been established by single crystal X-ray diffraction analyses. In the former, the two palladium atoms are held together by chloro and thiolato bridges whereas in the latter, the two phenylselenolato ligands bridge two palladium atoms. The pyrolysis of ${[Pd(\mu-TeMes)(C_10H_6NMe_2–C,N)]_2}$ (10) in a furnace gave {Pd_7Te_3} whereas thermolysis in TOPO afforded primarily {PdTe_2}.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to the Elsevier
Keywords: Palladium;Orthometallation;Organochalcogenolates;Structures;NMR
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 19 Jun 2008
Last Modified: 19 Sep 2010 04:46
URI: http://eprints.iisc.ernet.in/id/eprint/14370

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