The synthesis, structure and solution and gas phase properties of complexes of scandium and lanthanide triflates with the phosphine oxide ligands PhP(O)(C2H4P(O)Ph2)2 and P(O)(C2H4P(O)Ph2)3
The synthesis, structure and solution and gas phase properties of complexes of scandium and lanthanide triflates with the phosphine oxide ligands PhP(O)(C2H4P(O)Ph2)2 and P(O)(C2H4P(O)Ph2)3
The synthesis and structures of complexes of PhP(O)(C2H4P(O)Ph2)2, L1, and P(O)(C2H4P(O)Ph2)3, L2, respectively, with scandium and lanthanide triflates are described. Single crystal x-ray structures of complexes of the octahedral [Sc(L1)3](OTf)3, dodecahedral [Nd(OTf)(H2O)(L1)2](OTf)2 and [Ln(OTf)(H2O)(L2)2](OTf)2 (Ln = La, Gd), and the dimeric [{Er(OTf)2(H2O)(μ–L2)}2](OTf)2 and [{Er(OTf)2(EtOH)(μ–L2)}2](OTf)2, which have distorted pentagonal bipyramidal geometry around Er, have been determined. The solution properties of the complexes have been investigated by 19F and 31P NMR spectroscopy which show that the complexes of L1 are fluxional with exchange of inequivalent coordinated Ph2PO groups in solution. Complexes of L2 show the same process and exchange between coordinated and pendant arms of the ligand. The stability in the gas phase has been investigated by electrospray mass spectrometry (ESMS) and tandem ESMS where, in addition to loss of triflate, L1 and L2, loss of diphenylphosphine oxide and Ph2P(O)C2H4OSO2CF3 are shown to be significant decomposition pathways for complexes of both ligands. A brief study of the catalytic properties of a range of complexes shows that the alkenylation of 1,4-dimethoxybenzene with phenylacetylene in nitromethane does not occur at 80 °C for complexes of L1 or L2.
Electrospray mass spectrometrey, Lanthanide triflates, NMR spectroscopy, Polyphosphine oxide, Structure
Coles, Simon J.
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Hunter, Ann P.
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Fieldhouse, Sarah J.
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Lees, Anthony M.J.
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McCormick McPherson, Laura J.
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Platt, Andrew W.G.
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24 January 2025
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hunter, Ann P.
c0b6fe7d-4336-4cb0-a8ed-d6011343e7a4
Fieldhouse, Sarah J.
c03807d2-a231-4f5d-8ad4-157e1b1b4689
Lees, Anthony M.J.
d0525bcc-cbd9-4f7d-8a28-f4bb70f8d997
McCormick McPherson, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Platt, Andrew W.G.
1d1677ab-01a7-4a16-905b-4ce7a28f73d1
Coles, Simon J., Hunter, Ann P., Fieldhouse, Sarah J., Lees, Anthony M.J., McCormick McPherson, Laura J. and Platt, Andrew W.G.
(2025)
The synthesis, structure and solution and gas phase properties of complexes of scandium and lanthanide triflates with the phosphine oxide ligands PhP(O)(C2H4P(O)Ph2)2 and P(O)(C2H4P(O)Ph2)3.
Polyhedron, 269, [117395].
(doi:10.1016/j.poly.2025.117395).
Abstract
The synthesis and structures of complexes of PhP(O)(C2H4P(O)Ph2)2, L1, and P(O)(C2H4P(O)Ph2)3, L2, respectively, with scandium and lanthanide triflates are described. Single crystal x-ray structures of complexes of the octahedral [Sc(L1)3](OTf)3, dodecahedral [Nd(OTf)(H2O)(L1)2](OTf)2 and [Ln(OTf)(H2O)(L2)2](OTf)2 (Ln = La, Gd), and the dimeric [{Er(OTf)2(H2O)(μ–L2)}2](OTf)2 and [{Er(OTf)2(EtOH)(μ–L2)}2](OTf)2, which have distorted pentagonal bipyramidal geometry around Er, have been determined. The solution properties of the complexes have been investigated by 19F and 31P NMR spectroscopy which show that the complexes of L1 are fluxional with exchange of inequivalent coordinated Ph2PO groups in solution. Complexes of L2 show the same process and exchange between coordinated and pendant arms of the ligand. The stability in the gas phase has been investigated by electrospray mass spectrometry (ESMS) and tandem ESMS where, in addition to loss of triflate, L1 and L2, loss of diphenylphosphine oxide and Ph2P(O)C2H4OSO2CF3 are shown to be significant decomposition pathways for complexes of both ligands. A brief study of the catalytic properties of a range of complexes shows that the alkenylation of 1,4-dimethoxybenzene with phenylacetylene in nitromethane does not occur at 80 °C for complexes of L1 or L2.
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Accepted/In Press date: 7 January 2025
e-pub ahead of print date: 16 January 2025
Published date: 24 January 2025
Keywords:
Electrospray mass spectrometrey, Lanthanide triflates, NMR spectroscopy, Polyphosphine oxide, Structure
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Local EPrints ID: 499005
URI: http://eprints.soton.ac.uk/id/eprint/499005
ISSN: 0277-5387
PURE UUID: fb6d14bd-3fcc-4be2-bd32-e855d9354655
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Date deposited: 06 Mar 2025 17:56
Last modified: 22 Aug 2025 02:29
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Author:
Ann P. Hunter
Author:
Sarah J. Fieldhouse
Author:
Anthony M.J. Lees
Author:
Andrew W.G. Platt
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