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Tetradentate selenium ligand as a building block for homodinuclear complexes of Pd(II) and Ru(II) having seven membered rings or bis-pincer coordination mode: High catalytic activity of Pd-complexes for Heck reaction

1,2,4,5-Tetrakis(phenyselenomethyl)benzene (L) has been synthesized by reaction of in situ generated PhSe- with 1,2,4,5- tetrakis(bromomethyl)benzene in N2 atmosphere. Its first bimetallic complexes and a bis-pincer complex having compositions [(eta3- C3H5)2Pd2(L)][ClO4] 2 (1) [Pd2(C5H5N) 2(L)][BF4]2 (2) and [(eta6-C 6H6)2Ru2(L)Cl2][PF 6]2 (3) have been synthesized by reacting L with [Pd(eta3-C3H5)Cl]2, [Pd(CH 3CN)4][BF4]2 and [(eta6-C6H6)2RuCl 2]2 respectively. The structures of ligand L and its all three complexes have been determined by X-ray crystallography. In 1 and 3, ligand L forms with two organometallic species seven membered chelate rings whereas in 2 it ligates in a bis-pincer coordination mode. The geometry around Pd in 1 or 2 is close to square planar whereas in 3, Ru has pseudo-octahedral half sandwich “Piano-Stool” geometry. The Pd-Se bond distances are in the ranges 2.4004(9)-2.4627(14) A and follow the order 1 > 2, whereas Ru-Se bond lengths are between 2.4945(16) and 2.5157(17) A. The 1 and 2 have been found efficient catalysts for Heck reaction of aryl halides with styrene and methyl acrylate. The 2 is superior to 1. The TON and TOF values (per Pd) are up to ? 47500 and ?2639 h-1 respectively. The Royal Society of Chemistry 2010.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI