Lanthanide nitrate complexes of diphenylmethylphosphine oxide: synthesis and spectroscopic studies. Crystal structures of La(Ph2MePO)(3)(NO3)(3) , La(Ph2MePO)(4)(NO3)(3).xMe(2)CO and Yb(Ph2MePO)(4)(NO3)(2) PF6

Bosson, M., Levason, W., Patel, T., Popham, M. C. and Webster, M. (2001) Lanthanide nitrate complexes of diphenylmethylphosphine oxide: synthesis and spectroscopic studies. Crystal structures of La(Ph2MePO)(3)(NO3)(3) , La(Ph2MePO)(4)(NO3)(3).xMe(2)CO and Yb(Ph2MePO)(4)(NO3)(2) PF6. Polyhedron, 20 (15-16), 2055-2062. (doi:10.1016/S0277-5387(01)00796-3).

Abstract

The reaction of Ln(NO3)3·6H2O (Ln=lanthanide except Pm) with Ph2MePO in a 1:3 or 1:4 ratio in acetone or ethanol produces [Ln(Ph2MePO)3(NO3)3] which have been characterised by analysis, IR, 1H and 31P{1H} NMR spectroscopy and conductance measurements. The [Ln?(Ph2MePO)3(NO3)3] (Ln?=Pr–Tb) exist only as tris complexes in solution and are unaffected by the presence of excess Ph2MePO. In contrast the [Ln?(Ph2MePO)3(NO3)3] (Ln?=Ho–Lu) partially decompose in CH2Cl2 solution into [Ln?(Ph2MePO)4(NO3)2]+, and [Ln?(Ph2MePO)4(NO3)2]PF6 are readily isolated from Ln?(NO3)3, Ph2MePO and NH4PF6 in acetone. For lanthanum only, a neutral 1:4 complex [La(Ph2MePO)4(NO3)3] was isolated. X-ray crystal structures show that [La(Ph2MePO)3(NO3)3] contains nine-coordinate La, whilst [La(Ph2MePO)4(NO3)3]·xMe2CO contains a ten-coordinate metal centre. The structure of [Yb(Ph2MePO)4(NO3)2]PF6 reveals an eight-coordinate cation and all complexes contain bidentate nitrato-groups.

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Contributors

Author: W. Levason

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