A new series of five-co-ordinate rhenium(III) complexes containing the mixed S,P-bidentate 2-(diphenylphosphino)ethanethiolate ligand together with a monothiol RSH [R = Ph2PCH2CH2, Ph2P(O)CH2CH2, PhCH2, Ph or Pr(n)] have been synthesized and characterized. This Re(III)P2S3 series was prepared by substitution reactions of [Re(III)Cl3(MeCN)(PPh3)2], a pre-reduced rhenium(III) precursor, by addition of 2-(diphenylphosphino)ethanethiol and the corresponding monothiol. Formation of these compounds was verified by elemental analysis and H-1 and P-31 NMR and positive-ion fast atom bombardment mass spectroscopy. The complexes were found to be diamagnetic, neutral and stable. They exhibit a trigonal-bipyramidal geometry, where three sulfur atoms occupy the equatorial plane and two phosphorus atoms are positioned at the apices. The X-ray structural analysis of bis[2-(diphenylphoshino)ethanethiolato-kappaS,kappaP](phenylmethanethiol ato-kappaS)rhenium(III) revealed that this compound crystallizes in the monoclinic space group P2(1)/c with Z = 8, a = 21.011(9), b = 20.397(9), c = 16.289(7) angstrom, beta = 107.13(5)-degrees, R = 0.050, R' = 0.063, by using 5644 observed reflections. The above data further demonstrate the preference of a five-co-ordinate configuration when the P2S3 donor-atom set is available for co-ordinating rhenium(III).

Synthesis and characterization of five-co-ordinate rhenium(III) complexes with 2-(diphenylphosphino)ethanethiolate and monothiolate liqands. Crystal structure of [Re(Ph2PCH2CH2S)2(PhCH2S)]

DOLMELLA, ALESSANDRO;BANDOLI, GIULIANO;MAZZI, ULDERICO
1994

Abstract

A new series of five-co-ordinate rhenium(III) complexes containing the mixed S,P-bidentate 2-(diphenylphosphino)ethanethiolate ligand together with a monothiol RSH [R = Ph2PCH2CH2, Ph2P(O)CH2CH2, PhCH2, Ph or Pr(n)] have been synthesized and characterized. This Re(III)P2S3 series was prepared by substitution reactions of [Re(III)Cl3(MeCN)(PPh3)2], a pre-reduced rhenium(III) precursor, by addition of 2-(diphenylphosphino)ethanethiol and the corresponding monothiol. Formation of these compounds was verified by elemental analysis and H-1 and P-31 NMR and positive-ion fast atom bombardment mass spectroscopy. The complexes were found to be diamagnetic, neutral and stable. They exhibit a trigonal-bipyramidal geometry, where three sulfur atoms occupy the equatorial plane and two phosphorus atoms are positioned at the apices. The X-ray structural analysis of bis[2-(diphenylphoshino)ethanethiolato-kappaS,kappaP](phenylmethanethiol ato-kappaS)rhenium(III) revealed that this compound crystallizes in the monoclinic space group P2(1)/c with Z = 8, a = 21.011(9), b = 20.397(9), c = 16.289(7) angstrom, beta = 107.13(5)-degrees, R = 0.050, R' = 0.063, by using 5644 observed reflections. The above data further demonstrate the preference of a five-co-ordinate configuration when the P2S3 donor-atom set is available for co-ordinating rhenium(III).
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2495696
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