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Article

Bis(diphenylphosphino)methane Dioxide Complexes of Lanthanide Trichlorides: Synthesis, Structures and Spectroscopy

School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK
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Author to whom correspondence should be addressed.
Dedicated to Dr. Howard Flack (1943–2017).
Received: 18 October 2020 / Revised: 5 November 2020 / Accepted: 16 November 2020 / Published: 19 November 2020
Bis(diphenylphosphino)methane dioxide (dppmO2) forms eight-coordinate cations [M(dppmO2)4]Cl3 (M = La, Ce, Pr, Nd, Sm, Eu, Gd) on reaction in a 4:1 molar ratio with the appropriate LnCl3 in ethanol. Similar reaction in a 3:1 ratio produced seven-coordinate [M(dppmO2)3Cl]Cl2 (M = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), whilst LuCl3 alone produced six-coordinate [Lu(dppmO2)2Cl2]Cl. The complexes have been characterised by IR, 1H and 31P{1H}-NMR spectroscopy. X-ray structures show that [M(dppmO2)4]Cl3 (M = Ce, Sm, Gd) contain square antiprismatic cations, whilst [M(dppmO2)3Cl]Cl2 (M = Yb, Dy, Lu) have distorted pentagonal bipyramidal structures with apical Cl. The [Lu(dppmO2)2Cl2]Cl has a cis octahedral cation. The structure of [Yb(dppmO2)3(H2O)]Cl3·dppmO2 is also reported. The change in coordination numbers and geometry along the series is driven by the decreasing lanthanide cation radii, but the chloride counter anions also play a role. View Full-Text
Keywords: lanthanide trichloride complexes; diphosphine dioxide; coordination complexes; X-ray structures lanthanide trichloride complexes; diphosphine dioxide; coordination complexes; X-ray structures
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MDPI and ACS Style

Bannister, R.D.; Levason, W.; Reid, G. Bis(diphenylphosphino)methane Dioxide Complexes of Lanthanide Trichlorides: Synthesis, Structures and Spectroscopy. Chemistry 2020, 2, 947-959. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry2040060

AMA Style

Bannister RD, Levason W, Reid G. Bis(diphenylphosphino)methane Dioxide Complexes of Lanthanide Trichlorides: Synthesis, Structures and Spectroscopy. Chemistry. 2020; 2(4):947-959. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry2040060

Chicago/Turabian Style

Bannister, Robert D., William Levason, and Gillian Reid. 2020. "Bis(diphenylphosphino)methane Dioxide Complexes of Lanthanide Trichlorides: Synthesis, Structures and Spectroscopy" Chemistry 2, no. 4: 947-959. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry2040060

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