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

被引:0
作者
Coles, Simon J. [1 ]
Hunter, Ann P. [2 ]
Fieldhouse, Sarah J. [3 ]
Lees, Anthony M. J. [3 ]
Mcpherson, Laura J. McCormick [1 ]
Platt, Andrew W. G. [3 ]
机构
[1] Univ Southampton, UK Natl Crystallog Serv, Chem, Highfield Campus, Southampton SO17 1BJ, Hants, England
[2] Swansea Univ, Fac Med, Natl Mass Spectrometry Serv Facil, Hlth & Life Sci, Swansea SA2 8PP, England
[3] Staffordshire Univ, Sch Hlth Educ Policing & Sci, Leek Rd, Stoke On Trent ST4 2DF, England
基金
英国工程与自然科学研究理事会;
关键词
Lanthanide triflates; Structure; Polyphosphine oxide; NMR spectroscopy; Electrospray mass spectrometrey; CATALYTIC-PROPERTIES; TRIFLUOROMETHANESULFONATE;
D O I
10.1016/j.poly.2025.117395
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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)(mu-L2)}2](OTf)2 and [{Er(OTf)2(EtOH)(mu-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 degrees C for complexes of L1 or L2.
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共 36 条
  • [1] Shape maps and polyhedral interconversion paths in transition metal chemistry
    Alvarez, S
    Alemany, P
    Casanova, D
    Cirera, J
    Llunell, M
    Avnir, D
    [J]. COORDINATION CHEMISTRY REVIEWS, 2005, 249 (17-18) : 1693 - 1708
  • [2] Alvarez S., SHAPE-Program for the Stereochemical Analysis of Molecular Fragments by Means of Continuous Shape Measures and Associated Tools
  • [3] Three component synthesis of homoallylic amines. Efficient catalysis by lanthanum triflate/benzoic acid
    Aspinall, HC
    Bissett, JS
    Greeves, N
    Levin, D
    [J]. TETRAHEDRON LETTERS, 2002, 43 (02) : 323 - 325
  • [4] Solubilized lanthanide triflates:: Lewis acid catalysis by polyether and poly(ethylene glycol) complexes of Ln(OTf)3
    Aspinall, HC
    Dwyer, JLM
    Greeves, N
    McIver, EG
    Woolley, JC
    [J]. ORGANOMETALLICS, 1998, 17 (09) : 1884 - 1888
  • [5] Complexes of triphenylphosphine oxide with lanthanide bromides
    Bowden, Allen
    Platt, Andrew W. G.
    Singh, Kuldip
    Townsend, Rachel
    [J]. INORGANICA CHIMICA ACTA, 2010, 363 (01) : 243 - 249
  • [6] Dinuclear Eu+3 and Tb+3 complexes based on 1,2,4,5-tetrakis(diphenylphosphinyl)-benzene: Synthesis and luminescence properties
    Brel, V. K.
    Fedorov, Yu. V.
    Vologzhanina, A. V.
    Dorovatovskii, P. V.
    [J]. INORGANIC CHEMISTRY COMMUNICATIONS, 2022, 146
  • [7] Changing and challenging times for service crystallography
    Coles, Simon J.
    Gale, Philip A.
    [J]. CHEMICAL SCIENCE, 2012, 3 (03) : 683 - 689
  • [8] An [FeIII8] molecular oxyhydroxide
    Cutler, Daniel J.
    Coletta, Marco
    Singh, Mukesh K.
    Canaj, Angelos B.
    McCormick, Laura J.
    Coles, Simon J.
    Schnack, Jurgen
    Brechin, Euan K.
    [J]. DALTON TRANSACTIONS, 2022, 51 (23) : 8945 - 8948
  • [9] A P-31 NMR SPECTROSCOPIC STUDY OF COMPLEXATION OF TIN(II) AND LEAD(II) BY SOME PHOSPHINES, PHOSPHINE OXIDES, AND RELATED LIGANDS, WITH THE P-31 NUCLEAR MAGNETIC-RESONANCE SPECTRA OF 2 TETRATERTIARY PHOSPHINE TETRA-OXIDES AND THE ANALOGOUS TETRA-SULFIDES AND SELENIDES
    DEAN, PAW
    PHILLIPS, DD
    POLENSEK, L
    [J]. CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1981, 59 (01): : 50 - 61
  • [10] Electrospray mass spectrometry (ESI-MS) in the study of metal-ligand solution equilibria
    Di Marco, VB
    Bombi, GG
    [J]. MASS SPECTROMETRY REVIEWS, 2006, 25 (03) : 347 - 379