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
Simon J. Coles , Ann P. Hunter , Sarah J. Fieldhouse , Anthony M.J. Lees , Laura J. McCormick McPherson , Andrew W.G. Platt
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引用次数: 0
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.
期刊介绍：
Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry.
Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.
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