Base-Induced Coordination of a Prototypical Phosphenium Cation to Gallium Trichloride

Burford, Neil; Losier, Pierre; Sereda, S. V.; Cameron, T. Stanley; Wu, Gang

doi:10.1021/ja00093a074

Cited by 36 publications

(19 citation statements)

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“…32 Moreover, a related bismuthenium example has been isolated, 33 and complexes of phosphenium and arsenium cations have been realized. 31,34,35 By adjusting the sampling cone (SC) voltage of the Quattro mass spectrometer, we were able to effect the acceleration of ions through the region of intermediate pressure where ionmolecule collisions result in a declustering of the solvent molecules and, in the limit, collision-induced decomposition of the ions. For APCI experiments with 1, 2, 4, and 5, at an SC voltage of 30 V (typical operating condition) the bismuthenium cation [M -Cl] + is the base peak with a small peak (∼10% relative intensity) representing [(DMSO)M -Cl] + .…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

Agócs¹,

Burford²,

Cameron³

et al. 1996

J. Am. Chem. Soc.

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General, high-yield metathesis reactions provide two related and comprehensive series of dithiabismuth heterocycles. The compounds are characterized by spectroscopic and X-ray crystallographic analysis. Monocycles 4), and 2-chloro-1,3-dithia-6-oxa-2-bismocane (5) are kinetically stable with respect to the tethered bicyclic derivatives 1,2-bis((1,3-dithia-2-bismolan-2-yl)thio)ethane ( 6), 1,3-bis((1,3-dithia-2-bisman-2yl)thio)propane ( 7), 1,4-bis((1,3-dithia-2-bismepan-2-yl)thio)butane (8), bis((1,3,6-trithia-2-bismocan-2-yl)thio)ethyl) sulfide ( 9), and bis(((1,3-dithia-6-oxa-2-bismocan-2-yl)thio)ethyl) ether (10). Mass spectrometry provides an excellent means of characterization of compounds of this nature and is responsible for the identification of monocyclic bismuthenium cations as general and dominant dissociation products. In addition, the atmospheric pressure chemical ionization technique reveals solvent coordination chemistry of the bismuthenium cations.

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Section: Resultsmentioning

confidence: 99%

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

Agócs¹,

Burford²,

Cameron³

et al. 1996

J. Am. Chem. Soc.

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“…The σ 2 -phosphorus atom of 1 can extend its coordination number up to six without destruction of the four-membered ring skeleton. This is not surprising for compounds 1 − 8 since ring opening through breaking of the P−P bond would generate a stable bis(amino)phosphine on one side but an unstable low-coordinate phosphorus moiety on the other (a free or coordinated phosphinidene, , a phosphenium ion, , a selenexophosphane, , a diselenexophosphorane, ,, a dioxophosphorane, , and a coordinated oxophosphane, , respectively). Interestingly, derivative 7 can be regarded as a donor-stabilized dioxophosphorane (metaphosphate), 23a, a class of compound which has never been characterized by an X-ray diffraction study.…”

Section: Discussionmentioning

confidence: 99%

“…For compounds 9 − 11 , one might expect that ring cleavage should occur since, on both sides, a stable phosphorus entity would be generated: a bis(amino)phosphine and a phosphonium ion, a phosphorane, and a coordinated phosphine, respectively. Although a few examples of P−P interactions between phosphines and phosphonium ions, or even phosphoranes 26b, are known, derivative 11 is certainly the first compound featuring an interaction between a free and a coordinated phosphine 20b), except the P(2)O(2) bond [2.017(6) Å] which is one of the longest PO bonds known so far.…”

Section: Discussionmentioning

confidence: 99%

1σ⁴,2σ^x-Diphosphetes (x = 2−6): On the Persistence of the P−P Bond

et al. 1997

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Irradiation of [bis(diisopropylamino)phosphino](trimethylsilyl)diazomethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1σ4,2σ2-diphosphete 1 in 90% yield. Derivative 1 reacts with Fe2(CO)9 and W(CO)5(THF) giving rise to the corresponding η1-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 equiv of methyl trifluoromethanesulfonate and elemental selenium is added to derivative 1, the cationic and neutral 1σ4,2σ3-diphosphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addition of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide to diphosphete 1 gave rise to 1σ4,2σ4-diphosphetes 6 (43% yield) and 7 (84% yield), respectively. η1-(1σ4,2σ2-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)peroxide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1σ4,2σ3-diphosphete 4 and of 2 equiv to the 1σ4,2σ2-diphosphete 1 affords the 1σ4,2σ5- and 1σ4,2σ6-diphosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of TCBQ to the η1-(1σ4,2σ2-diphosphete)tungsten complex 3 affords the η1-(1σ4,2σ4-diphosphete)complex 11 (88% yield), which reacts with 2 equiv of trimethylphosphine leading to the zwitterionic 1σ4,2σ3-diphosphete 12 (46% yield). Cleavage of the Si−C bond of complex 3 with 1 equiv of tetrabutylammonium fluoride hydrate gives η1-(1σ4,2σ2-diphosphete)complex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-diphosphino alkene complex 14 (77% yield). These results demonstrate that the unsaturated four-membered ring skeleton is a remarkable template for inducing unusual P−P interactions. However, the presence of two very bulky substituents on the ethylenic moiety is necessary for the persistence of the cyclic structure, when the two phosphorus atoms feature a high coordination state. Single crystal X-ray diffraction studies of derivatives 7 and 11−14 have been carried out.

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“…The potential for the phosphine centre in phosphinophosphonium cations to behave as a donor is demonstrated (Scheme 6a) by the isolation of [Me 2 ClPP(Me 2 )GaCl 3 ] 1+ , 56 spectroscopic characterization of related [RCl 2 PP(R)(Cl)GaCl 3 ] 1+ cations, 57 and isolation of transition metal complexes like the Scheme 4 Proposed mechanism for insertion of phosphenium cations into P-P bonds. tungsten complex of a cyclic phosphinophosphonium (Scheme 6b).…”

Section: Coordination and Oxidation Of Lone Pair Bearing Acceptor-cenmentioning

confidence: 99%

Phosphine complexes of lone pair bearing Lewis acceptors

Chitnis

Burford

2015

Dalton Trans.

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An overview of the synthesis, structures and reaction chemistry of coordination complexes featuring an acceptor with at least one lone pair and at least one phosphine donor is presented. One or more examples of complexes have been structurally-characterized for the majority of p-block elements but few are known for most elements. The unusual condition of a p-block element centre accommodating a lone pair of electrons and offering a low energy LUMO gives the element centre the potential to behave as both a Lewis acid and a Lewis Base. The structural diversity and reactivity of the phosphine complexes highlights new directions in main group chemistry and by comparison with transition metal coordination chemistry, the featured complexes demonstrate significant configurational and stereochemical flexibility. Ligand exchange, oxidation and reduction chemistry at the lone pair bearing acceptor centre reveals unusual reactivity and an interesting class of ligands and inorganic reagents, with new possibilities for catalysis or small molecule activation.

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Base-Induced Coordination of a Prototypical Phosphenium Cation to Gallium Trichloride

Cited by 36 publications

References 0 publications

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

1σ⁴,2σ^x-Diphosphetes (x = 2−6): On the Persistence of the P−P Bond

Phosphine complexes of lone pair bearing Lewis acceptors

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Base-Induced Coordination of a Prototypical Phosphenium Cation to Gallium Trichloride

Cited by 36 publications

References 0 publications

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

1σ4,2σx-Diphosphetes (x = 2−6): On the Persistence of the P−P Bond

Phosphine complexes of lone pair bearing Lewis acceptors

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Product

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1σ⁴,2σ^x-Diphosphetes (x = 2−6): On the Persistence of the P−P Bond