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Soft diphosphine and diarsine complexes of niobium(V) and tantalum(V) fluorides: synthesis, properties, structures and comparisons with the corresponding chlorides
The reactions of the soft diphosphines o-C6H4(PMe2)2, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2 or o-C6H4(PPh2)2 with NbF5 or TaF5 in anhydrous MeCN solution produce [MF4(diphosphine)2][MF6] (M = Nb or Ta), which have been characterised by microanalysis, IR, (1)H, (19)F{(1)H}, (31)P{(1)H} and (93)Nb NMR spectr...
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Published in: | Dalton transactions : an international journal of inorganic chemistry 2014-07, Vol.43 (25), p.9557-9566 |
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Main Authors: | , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | The reactions of the soft diphosphines o-C6H4(PMe2)2, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2 or o-C6H4(PPh2)2 with NbF5 or TaF5 in anhydrous MeCN solution produce [MF4(diphosphine)2][MF6] (M = Nb or Ta), which have been characterised by microanalysis, IR, (1)H, (19)F{(1)H}, (31)P{(1)H} and (93)Nb NMR spectroscopy. X-ray crystal structures are reported for the isomorphous [MF4{o-C6H4(PMe2)2}2][MF6], which confirm the presence of eight-coordinate (distorted dodecahedral) cations. The corresponding reactions using o-C6H4(AsMe2)2 produced [MF4{o-C6H4(AsMe2)2}2][MF6] which were similarly characterised, including by the X-ray structure of [NbF4{o-C6H4(AsMe2)2}2][NbF6]. These are very rare examples of arsine complexes of high valent metal fluorides. The chloro complexes [NbCl4{o-C6H4(PMe2)2}2]Cl, [TaCl4{o-C6H4(PMe2)2}2][TaCl6], [NbCl4{Me2P(CH2)2PMe2}2][NbCl6] and [MCl4{o-C6H4(AsMe2)2}2][MCl6] were prepared and their structural and spectroscopic properties compared with the fluoride analogues. Attempts to prepare diphosphine complexes of NbOF3 were unsuccessful, but the NbOCl3 complexes, [{{Me2P(CH2)2PMe2}NbOCl3}2{μ-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(μ-O)NbCl3(CH3CN){o-C6H4(PMe2)2}] were obtained. X-Ray structures are also reported for [NbCl4{o-C6H4(PMe2)2}2]Cl, [NbCl4{o-C6H4(AsMe2)2}2][NbCl5(OEt)], [NbCl4{o-C6H4(PMe2)2}2][NbOCl4(CH3CN)], [{{Me2P(CH2)2PMe2}NbOCl3}2{μ-Me2P(CH2)2PMe2}] and [{o-C6H4(PMe2)2}NbOCl3(μ-O)NbCl3(CH3CN){o-C6H4(PMe2)2}]. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c4dt01029a |