Bismuth(III) Chloride Complexation with Diphosphine and Diarsine Oxide Ligands: Formation and Crystal Structures of >2 and >n

DOI: 10.1039/DT9950000759

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 759 - 764 (1995)

Update date:2022-08-04

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Authors:

Willey, Gerald R.

Rudd, Martin D.

Samuel, Christopher J.

Drew, Michael G. B.

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Article abstract of DOI:10.1039/DT9950000759

The reactions of bismuth(III) chloride and Ph2PCH2PPh2 (dppm) and Ph2AsCH2CH2AsPh2 (dpae) have been studied.The yellow products isolated initially were characterised by spectroscopic (1H and 31P NMR, IR) and microanalytical data as the 1:1 addition compounds BiCl3*dppm and BiCl3*dpae respectively.Recrystallisation of these products from boiling acetonitrile/charcoal effected oxidation of the ligands and resulted in the formation of two new molecular adducts whose structures have been determined by X-ray crystallography.Crystals of >2 1 are triclinic, space group P<*> with Z = 2.There are two independent centrosymmetric molecules in the unit cell with similar egde-edge shared bioctahedral structures.Each bismuth centre is six-co-ordinate with approximal octahedral geometry being bonded to two terminal chlorine atoms, two bridging chlorine atoms and two oxygen (ligand) atoms.In situ ligand oxidation dppm ---> Ph2P(O)CH2P(O)Ph2 occurs and the resulting bidentate (OO') chelation gives rise to puckered six-membered ring formation.Crystals of >n 2 are monoclinic, space group P2₁/a with Z = 4.The structure consists of one-dimensional polymeric chains.Here the in situ ligand oxidation is more complex and results in the formation of two arsine oxide ligands, viz. dpae ---> Ph2As(O)CH2CH2As(O)Ph2 + As(O)MePh2 both of which are involved in co-ordination to Bi(III).Each bismuth atom is bonded in an approximately mer-octahedral arrangement to three terminal chlorine atoms, and three oxygen (ligand) atoms.Of the latter, one is provided by a monodentate As(O)MePh2 molecule and the other two by separate Ph2As(O)CH2CH2As(O)Ph2 molecules which, by virtue of their bidentate bridging mode, are linked to adjacent metal centres.

Full text of DOI:10.1039/DT9950000759

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