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Diphosphine dioxide complexes of lanthanum and lutetium – the effects of ligand architecture and counter-anion

Diphosphine dioxide complexes of lanthanum and lutetium – the effects of ligand architecture and counter-anion
Diphosphine dioxide complexes of lanthanum and lutetium – the effects of ligand architecture and counter-anion
The reaction of bis(diphenylphosphino)methane dioxide (dppmO2) with LaCl3, LaI3 or LaCl3/[NH4][PF6] produces [La(dppmO2)4]Y3 (Y = Cl, I, PF6) which contain eight-coordinate, distorted square antiprismatic cations. In contrast, LaCl3 or LaCl3/[NH4][PF6] and 1,2-bis(diphenylphosphino)ethane dioxide (dppeO2) produce the polymer [LaCl3(dppeO2)1.5]n, which has a six-coordinate La centre with three mer-chlorides and three Ph2P(O)CH2-donors from three different diphosphine dioxide ligands. The bulkier 1,2-bis (diphenylphosphino)benzene dioxide (PPO2) forms [LaCl2(PPO2)2(H2O)2]Cl and [LaCl2(PPO2)2(H2O)2]
[PF6], which contain eight-coordinate La, and also the seven-coordinate [LaCl(PPO2)3][PF6]2. The smaller lutetium ion favours six-coordination in [LuCl2(dppmO2)2]Cl, [LuI2(dppmO2)2]I, [LuCl(dppmO2)2(H2O)] [PF6]22H2O, [LuCl2(PPO2)2]Cl, [LuI2(PPO2)2]I and [Lu(PPO2)2(H2O)2][PF6]3. All complexes were characterised by microanalysis, IR, 1H and 31P{1H} NMR spectroscopy. X-ray crystal structures are reported for [La(dppmO2)4]Y3 (Y = I, PF6), [LaCl3(dppeO2)1.5]n, [LaCl2(PPO2)2(H2O)(EtOH)]Cl and [LaCl(PPO2)3][PF6]2.
Diphosphine dioxide, lanthanum, lutetium, x-ray structures, 31P NMR spectroscopy
0277-5387
264-269
Bannister, Robert, David
4dd3eb2a-5ba7-46de-9277-8dd7e8e39b74
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Bannister, Robert, David
4dd3eb2a-5ba7-46de-9277-8dd7e8e39b74
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Bannister, Robert, David, Levason, William, Reid, Gillian and Zhang, Wenjian (2017) Diphosphine dioxide complexes of lanthanum and lutetium – the effects of ligand architecture and counter-anion. Polyhedron, 133, 264-269. (doi:10.1016/j.poly.2017.04.039). (In Press)

Record type: Article

Abstract

The reaction of bis(diphenylphosphino)methane dioxide (dppmO2) with LaCl3, LaI3 or LaCl3/[NH4][PF6] produces [La(dppmO2)4]Y3 (Y = Cl, I, PF6) which contain eight-coordinate, distorted square antiprismatic cations. In contrast, LaCl3 or LaCl3/[NH4][PF6] and 1,2-bis(diphenylphosphino)ethane dioxide (dppeO2) produce the polymer [LaCl3(dppeO2)1.5]n, which has a six-coordinate La centre with three mer-chlorides and three Ph2P(O)CH2-donors from three different diphosphine dioxide ligands. The bulkier 1,2-bis (diphenylphosphino)benzene dioxide (PPO2) forms [LaCl2(PPO2)2(H2O)2]Cl and [LaCl2(PPO2)2(H2O)2]
[PF6], which contain eight-coordinate La, and also the seven-coordinate [LaCl(PPO2)3][PF6]2. The smaller lutetium ion favours six-coordination in [LuCl2(dppmO2)2]Cl, [LuI2(dppmO2)2]I, [LuCl(dppmO2)2(H2O)] [PF6]22H2O, [LuCl2(PPO2)2]Cl, [LuI2(PPO2)2]I and [Lu(PPO2)2(H2O)2][PF6]3. All complexes were characterised by microanalysis, IR, 1H and 31P{1H} NMR spectroscopy. X-ray crystal structures are reported for [La(dppmO2)4]Y3 (Y = I, PF6), [LaCl3(dppeO2)1.5]n, [LaCl2(PPO2)2(H2O)(EtOH)]Cl and [LaCl(PPO2)3][PF6]2.

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Accepted/In Press date: 30 April 2017
Keywords: Diphosphine dioxide, lanthanum, lutetium, x-ray structures, 31P NMR spectroscopy

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Local EPrints ID: 412784
URI: http://eprints.soton.ac.uk/id/eprint/412784
ISSN: 0277-5387
PURE UUID: d81ff563-11bc-4acd-94a8-61d2692a3c9e
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 01 Aug 2017 16:31
Last modified: 26 Nov 2019 02:07

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Contributors

Author: Robert, David Bannister
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Wenjian Zhang

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