Lanthanide halide and nitrate complexes with potentially tridentate bisphosphine dioxide – ether donors

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Abstract Complexes of the bisphosphine dioxide ethers, bis[(2-diphenylphosphino)phenyl]ether dioxide (I) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthane dioxide (II) with lanthanide chlorides, bromides and nitrates have been synthesised, giving LnX3(I)2(H2O)n and LnX3(II)2(H2O)n X = NO3, Cl, Br. The structures of the complexes of PrCl3 and NdCl3 with (I) and LaCl3 and LaBr3 with (II) are reported. These complexes are ionic [LnX2(I)2]+X−, [LnX2(II)2]+X− and show the effect of flexibility in the ligand structure with (I) able to coordinate through one of its ether oxygen atoms, whilst (II) bonds through the phosphoryl oxygens only. The infrared spectra of the nitrates indicate that Ln(NO3)3(I)2 contain monodentate nitrate whilst in Ln(NO3)3(II)2 the nitrates are bidentate.