Investigations into cerium(III) and cerium(IV) nitrate complexes with tris-1-naphthylyphosphine oxide and bis-1-naphthlyalklyphosphine oxides

Abstract

The reaction between ammonium cerium(IV) nitrate (CAN) and tris-1-naphthylphosphine oxide (Nap3PO, L1), bis-1-naphthylmethlyphosphine oxide (Nap2MePO, L2) and bis-1-naphthylethlyphosphine oxide (Nap2EtPO, L3) have been investigated. The 31P NMR spectra show that complex formation occurs readily in CD3CN solution and more slowly in CDCl3. Isolation of bulk Ce(IV) complexes was difficult due to decomposition to Ce(III) during crystallisation. The Ce(IV) complexes can be characterised in solution by multinuclear NMR (1H, 13C and 31P) spectroscopy and show that decomposition to Ce(III) occurs in CD3CN with Ce(IV) being more stable in CDCl3. The structures of the ligands Nap2MePO and Nap2EtPO and the complexes [Ce(NO3)3(Nap2MePO)3], [Ce(NO3)3(Nap2EtPO)3] and [Ce(NO3)4(Nap2EtPO)2] have been determined. Ce(IV) solutions undergo reduction to Ce(III) during the electrospray ionisation mass spectra process. The tandem mass spectra of [Ce(NO3)2Ln]+ show that loss of ligand is favoured for for high values of n whilst for n = 2 loss of NO2 generating Ce(IV) oxo complexes is increasingly important.

More information

Identifiers

ORCID for Simon J. Coles: orcid.org/0000-0001-8414-9272

ORCID for Laura McCormick McPherson: orcid.org/0000-0002-6634-4717

Catalogue record

Export record

Altmetrics