UNSPECIFIED (1996) Phosphorus donor complexes of bismuth(III). Structural characterisation of [Bi2Cl6(Ph(2)PCH(2)PPh(2))(2)], [Bi2Cl6(Ph(2)PCH(2)CH(2)PPh(2))(2)] and [Bi2Cl6(Ph(2)PCH(2)CH(2)PPh(2))(3)]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (6). pp. 1063-1067. ISSN 0300-9246

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Abstract

The reactions of the diphosphines dppm [bis(diphenylphosphino)methane] and dppe [1,2-bis(diphenylphosphino)ethane] with bismuth(III) chloride in acetonitrile solution have been studied. The resulting complexes [Bi2Cl6(dppm)(2)] 1 and [Bi4Cl12(dppe)(5)] 2 respectively, have been-structurally identified by X-ray diffraction studies. The centrosymmetric structure 1 . 2MeCN consists of coplanar halide-bridged Bi2Cl6 units with each of the two dppm ligand molecules in a bidentate bridging mode between the two metal sites. The overall co-ordination geometry at each bismuth atom is approximately octahedral with four (equatorial) chlorine atoms and two (axial) phosphorus atoms: Bi-Cl (terminal) 2.475(3), 2.530(4), Bi-Cl (bridging) 2.808(4), 2.820(3), Bi-P 2.872(3), 3.090(3) Angstrom. In 2 there are two separate and independent molecules in the asymmetric unit cell identified as [Bi2Cl6(dppe)(2)] 2a and [Bi2Cl6(dppe)(3)] 2b respectively. For 2a the centrosymmetric structure is made up of halide-bridged Bi2Cl6 units with bidentate chelate attachment of a dppe ligand molecule to each bismuth atom giving rise to an overall edge-shared bioctahedral geometry: Bi-Cl (terminal) 2.409(9), 2.470(11), Bi-Cl (bridging) 2.619(9), 2.945(9), Bi-P 2.699(8), 2.956(10)Angstrom. In the case of 2b the centrosymmetric dimer contains two BiCl3(dppe) moieties connected by a bridging dppe ligand; thus both bidentate chelate and bidentate bridging bonding modes are observed, Each bismuth atom is surrounded by three terminal chlorine atoms, Bi-Cl 2.514(8), 2.521(9), 2.555(9)Angstrom, and three phosphorus atoms, two from the chelating ligand, Bi-P 2.654(8), 2.916(9)Angstrom, and one from the bridging ligand, Bi-P 2.973(9)Angstrom, in an approximately mer-octahedral arrangement.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	0300-9246
Date:	21 March 1996
Number:	6
Number of Pages:	5
Page Range:	pp. 1063-1067
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/18954

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