Synthesis of transition-metal complexes with heterodifunctional ligands derived of NH(PPh<sub>2</sub>)<sub>2</sub>.: Crystal structure of [(η<SUP>5</SUP>-C<sub>5</sub>Me<sub>5</sub>)RhCl{η<SUP>2</SUP>-<i>P</i>, <i>Se</i>-Ph<sub>2</sub>PNP(Se)Ph<sub>2</sub>}]•CH<sub>2</sub>Cl<sub>2</sub>
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Date
2001
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Abstract
The uncoordinated P atom of the bis(diphenylphosphine)amine (dppa) ligand in complexes [(ring)MCl2(eta (1)-P-PPh2NHPPh2)] (M = Rh, Ir. Ru) reacts with sulphur or selenium to form [(ring)MCl2(eta (1)-P-PPh2-NHP(E)Ph-2)] (E = S (1-3), Se (4-6)) containing the P-coordinated monosulphide or monoselenide ligands. The selenium derivatives have also been directly prepared from the corresponding [{(ring)MCl2)(2)] dimer and dppaSe. Chloride abstraction from rhodium and ruthenium complexes gives the neutral compounds [(ring)MCl(eta (2)-P,E-PPh2NP(E)Ph-2)] (7-10) whilst the iridium derivatives yield cationic complexes of the general formula [{eta (5)-C5Me5)IrCl(eta (2)-P,E-PPh2NHP(E)Ph-2)](+) (11 and 12). The crystal structure of complex [(eta (5)-C5Me5)RhCl{eta (2)-P,SePPh2NP(Se)Ph-2}] has been established by X-ray crystallography. The rhodium atom exhibits a distorted octahedral coordination with a eta (5)-C5Me5 group occupying the centre of three octahedral sites, a bidentate chelate P,Se-bonded ligand and a chloride atom complete the metal coordination sphere. (C) 2001 Elsevier Science B.V. All rights reserved.
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rhodium, iridium, ruthenium, Bis(diphenylphosphine)amine complexes, monochalcogenide complexes