The oxidation of dimethyl sulphide, trimethylamine, and trimethylphosphine by solvated copper(II) or thallium(III) hexafluorometallates in acetonitrile

Siddique, Rana M.; Winfield, John M.

doi:10.1139/v89-275

Cited by 25 publications

(24 citation statements)

References 15 publications

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“…A single crystal isolated from this mixture at À35 8C was shown by X-ray crystallography to be a cocrystalline mixture of the stibinotriphosphonium salt 4[OTf] 3 Reductive elimination of diphosphonium dications from metal phosphine complexes has been proposed previously as the mechanism responsible for the observation of [Me 3 PPMe 3 ] 2+ from the decomposition of trimethylphosphine complexes of Cu II and Tl III , which also yields the corresponding reduced Cu I and Tl I species. [15] Moreover, the dimerization of an in situ generated neutral stibinidene (RSb) to give an isolable distibene (RSb=SbR) has been observed previously, [16] and we expect the cationic stibinidene derivative postulated here ([Me 3 PSb] + ) to be even more reactive towards dimerization because of its enhanced electrophilicity.…”

Section: +supporting

confidence: 68%

Assembly of a cyclo‐Tetrastibinotetraphosphonium Tetracation by Reductive Elimination

et al. 2013

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Electron-rich (lone-pair bearing) non-metal elements offer a potentially diverse coordination chemistry as acceptors, and this chemistry is enhanced by the presence of a cationic charge which augments the Lewis acidity at the acceptor site. As such, the coordination chemistry of non-metals offers new synthetic and structural opportunities with guidance from established coordination chemistry of transition metals, and with the possibility of catenation of the nonmetal. For example, the maximally charged Sb 3+ trication can engage a crown ether [1] or two 2,2-bipyridine (bipy) ligands. [2] While phosphine ligands are also expected to support the Sb 3+ cation, we have discovered that the redox activity between antimony and phosphorus results in formation of an unusual cyclo-tetrastibinotetraphosphonium salt.Addition of three equivalents of trimethylsilyltrifluoromethanesulfonate (TMSOTf) to a suspension of SbF 3 in acetonitrile results in immediate gaseous evolution of Me 3 SiF. After the subsequent addition of PMe 3 and heating to reflux for 30 minutes, the 31 P, 1 H, and 13 C NMR spectra of the clear yellow reaction mixture show quantitative formation of [Me 3 PPMe 3 ][OTf] 2 ( 31 P NMR: d = 28.4 ppm; 1 H NMR: d = 2.39 ppm; 13 C NMR: d = 7.10 ppm), [3] and a new compound characterized as [(Me 3 P) 4 Sb 4 ][OTf] 4 (1[OTf] 4 ; 31 P NMR: d = À24.5 ppm). Identical NMR spectral features are observed for the mixtures of [bipy 2 Sb][OTf] 3 or Sb(OTf) 3 and PMe 3 in a 1:3 ratio at room temperature. It was not possible to separate 1[OTf] 4 from its crystalline mixture with [Me 3 PPMe 3 ][OTf] 2 . In comparison, mixtures of [bipy 2 SbF]-[OTf] 2 or FSb(OTf) 2 and PMe 3 in a 1:2 ratio at 25 8C give 1[OTf] 4 and [Me 3 PF][OTf] ( 31 P NMR: d = 148 ppm; 19 F NMR: d = À138 ppm). [11] Upon cooling this reaction mixture to À30 8C, fractional crystallization affords yellow crystals of 1[OTf] 4 ·3 CH 3 CN.

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Section: +supporting

confidence: 68%

Assembly of a cyclo‐Tetrastibinotetraphosphonium Tetracation by Reductive Elimination

et al. 2013

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“…The most investigated solvent in Cu I /Cu II ÀMF 5 (M = P, As, Sb, Nb, Ta, Mo, W or U) system is acetonitrile (CH 3 CN) [11][12][13][14][15][16][17][18]. The Cu II /Cu I cations are solvated by CH 3 CN as in solution as in isolated products.…”

Section: Resultsmentioning

confidence: 99%

“…; X À = [PF 6 ] À , [AsF 6 ] À , [MoF 6 ] À , [UF 6 ] À , [BF 4 ] À , etc.) [11][12][13][14][15][16][17][18] are not included, because in their case Cu I is coordinated by organic ligands and expected to be well separated from fluorine containing anions (X À ).…”

Section: Introductionmentioning

confidence: 99%

Copper(I) hexafluoroantimonate – an example of a compound with CuI in a solely fluorine environment

Mazej

Benkič

2005

Journal of Fluorine Chemistry

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“…Hexaalkyldiphosphonium triiodide salts were speculated as the products of reactions of red phosphorus with alkyl iodides or from trialkylphosphanes with iodine, 143 and [Me 3 PPMe 3 ][PF 6 ] 2 (96 2+ , R = R 0 = Me) has first been assigned on the basis of elemental analysis data and IR spectroscopy. 144 Polyphosphane adducts of electrophilic antimony, 145 thallium, 144 copper, 144 or iron 146…”

Section: Bonding Motif Lmentioning

confidence: 99%

Recent highlights in mixed-coordinate oligophosphorus chemistry

2016

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This review aims to highlight and comprehensively summarize recent developments in the field of mixed-coordinate phosphorus chemistry. Particular attention is focused on the synthetic approaches to compounds containing at least two directly bonded phosphorus atoms in different coordination environments and their unexpected properties that are derived from spectroscopic and crystallographic data. Novel substance classes are discussed in order to supplement previous reviews about mixed-coordinate phosphorus compounds.

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The oxidation of dimethyl sulphide, trimethylamine, and trimethylphosphine by solvated copper(II) or thallium(III) hexafluorometallates in acetonitrile

Cited by 25 publications

References 15 publications

Assembly of a cyclo‐Tetrastibinotetraphosphonium Tetracation by Reductive Elimination

Assembly of a cyclo‐Tetrastibinotetraphosphonium Tetracation by Reductive Elimination

Copper(I) hexafluoroantimonate – an example of a compound with CuI in a solely fluorine environment

Recent highlights in mixed-coordinate oligophosphorus chemistry

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