283. The preparation of di- and tri-tertiary phosphines

Hewertson, W.; Watson, H. R.

doi:10.1039/jr9620001490

Cited by 253 publications

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“…The this solution, a slight excess of 3-butyn-1-ol (23 µl, 0.30 mmol) was ligand CH 3 C(CH 2 PPh 2 ) 3 (triphos) [28] and the complexes [(triphos)-added with stirring, and the solution was slowly brought to room Re(CO) 2 H] (1) [19] and [(triphos)Re(CO) 2 (η 2 -H 2 )]BF 4 (2) [20] were temperature. During this time, the color of the resulting solution prepared as described in the literature.…”

Section: Insmentioning

confidence: 99%

2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

Bianchini¹,

Marchi

Mantovani

et al. 1998

Eur. J. Inorg. Chem.

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Various β‐, γ‐, and δ‐alkynols have been reacted with the 16e− fragment [(triphos)Re(CO)2]+ generated in situ by H2 elimination from [(triphos)Re(CO)2(η2‐H2)]BF4 [triphos = MeC(CH2PPh2)3]. Irrespective of the length of the alkyl chain between the C≡C and OH functional groups in the ω‐alkynol, 2‐oxacyclocarbene complexes are obtained. These include the 2‐oxacyclopentylidene derivatives [(triphos)Re(CO)2{=CCH2CH2CH2O}]BF4 and [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]BF4, the 2‐oxacyclohexylidene dervivatives [(triphos)Re(CO)2{=CCH2CH2CH2CH2O}]BF4 and[(triphos)Re(CO)2{=CCH2CH2CH2CH(Me)O}]BF4, and the 2‐oxacycloheptylidene complex [(triphos)Re(CO)2{=CCH2CH2‐ CH2CH2CH2O}]BF4. The latter compound contains a unprecedented seven‐membered oxacarbene ring. The rhenium‐assisted δ‐alkynol to 2‐oxacyloheptylidene rearrangement proceeds via the hydroxybutylvinylidene kinetic intermediate [(triphos)Re(CO)2{C=C(H)CH2CH2CH2CH2OH}]BF4, which has been characterized in both the solid state and solution. An X‐ray analysis has been carried out on a single crystal of [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]BF4. The structure of this complex consists of [(triphos)Re(CO)2{=CCH2CH2CH(Me)O}]+ cations and tetrafluoroborate anions with no interspersed solvent molecules. A facial triphos ligand, two cis‐disposed carbonyl groups and a 2‐oxacyclopentylidene ligand coordinate the Re centre in a slightly distorted octahedral environment.

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Section: Insmentioning

confidence: 99%

2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

Bianchini¹,

Marchi

Mantovani

et al. 1998

Eur. J. Inorg. Chem.

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“…Literature methods were used in the synthesis and purification of 1,2-bis(dipheny1phosphino)ethane (22) and 1,4-bis(dipheny1phosphino)butane (23).…”

Section: Discussionmentioning

confidence: 99%

Nuclear magnetic resonance studies of the solvation of phosphorus(V) selenides, 1,2-bis(diphenylphosphino)ethane, and tris(dimethylamino)phosphine telluride by sulfur dioxide

Dean¹

1979

Can. J. Chem.

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PHILIP A. W. DEAN. Can. J. Chem. 57,754 (1979). 31P and 77Se nmr spectra have been measured for a range of phosphorus(V) selenides, diphosphorus(V) diselenides, and triphosphorus(V) triselenides in the inert solvent CH2C12 and in liquid SO,. Significant roughly-correlated reductions in IIJ(PSe)) and deshielding of the 77Se resonance accompany change of solvent from CH,Cl, to SO,. These changes are shown to arise from 1 : 1 phosphorus(V) selenide:S02 donor:acceptor complex formation. Approximate thermodynamic constants for the formation of the complexes have been determined and possible structures for the 1 : 1 complexes with the diphosphorus(V) diselenides discussed. It is shown from 'H and 31P nmr spectral changes that Ph,P(CH2),PPh2 forms a 1 : 1 complex with SOz, and approximate thermodynamic data for the SO, complexation of the diphosphine have been established. Complexation is indicated by changes in both I1J(PTe) and 6, when (Me2N)3PTe is dissolved in SO,, but the chemical reactivity of this system precluded detailed study.PHILIP A. W. DEAN. Can. J. Chem. 57,754 (1979). On a dttermint les spectres rmn du 31P et du 77Se d'un certain nombre de stltnures de phosphore(V), de distltnures de diphosphore(V) et de triskltnures de triphosphore(V) dans le solvant inerte CH,Cl, et dans le SO, liquide. Un changement de solvent de CH2C12 a SO, s'accompagne de rkductions marqutes qui prtsente une corrklation grossikre des IIJ(PSe)l et des dtblindages de la resonance du 77Se. On a montrt que ces changen~ents sont dus a la formation d'un complexe 1: 1 d0nneur:accepteur stltnure de phosphore(V):S02. On a dttermint les constantes thermodynamiques approximatives pour la formation des complexes et on discute des structures possibles des complexes 1 : 1 avec les distlenures de diphosphore. On a montrt, grace aux chailgements dans les spectres rmn du 'H et du 31P, que le PH2P(CH2)2PPH2 forme un complexe 1 : 1 avec le SO, et on a dttermint les donnkes thermodynamiques approximatives pour la complexation de la diphosphine par le SO,. La complexation est rtvtlte par des changements & la fois dans JIJ(PTe)l et dans le Sp lorsqu'on dissout du (Me2N)3PTe dans le SO,; la rtactivitt chimique de ce systkme ne permet par une ktude plus dttaillke.[Traduit par le journal]

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“…1,2-Bis(dipheny1phosphino)ethane was prepared by the standard method (17). Several of the phosphine oxides were prepared as part of an earlier study (18).…”

Section: Methodsmentioning

confidence: 99%

A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

Dean¹,

Phillips²,

Polensek³

1981

Can. J. Chem.

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31P nmr has been used to show that, in MeNO2, M(SbF6)2 (M = Sn or Pb) forms 1:1 complexes with Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, [Formula: see text][Formula: see text]P[(CH2)2PPh2]3, and Ph2P[(CH2)2PPh]2(CH2)2PPh2. The phosphonium ligands are formed in situ. Spectra characteristics of slow inter- and intramolecular exchange were obtained in all cases except, perhaps, those involving the last two ligands, which may be involved in rapid intramolecular exchange. For the first five ligands, the maximum denticity is achieved and unambiguous one-bond M(II)—31P (M = 117/119Sn or 207Pb) coupling constants are reported and discussed. In the presence of M(SbF6)2 (M = Sn or Pb). PPh3 is protonated in MeNO2, while in acetone Sn(SbF6)2 forms a 1:1 complex with PPh3 which appears to be solvent-inserted, [Sn—O—CMe2PPh3]2+.Reduced temperature 31P nmr spectroscopy has allowed the detection of 1:2 and 1:3 (M:L) complexes of OPPh3, and 1:1 complexes of Ph2P(O)(CH2)2P(O)Ph2, PhP(O)[(CH2)2P(O)Ph2]2, and (O)P[(CH2)2P(O)Ph2]3, with both tin(II) and lead(II). The 1:1 complexes with polydentate ligands are isolable; nmr shows that the maximum denticity occurs except with the last ligand which behaves in a tridentate manner. Several two-bond M—O—P coupling constants have been obtained. Also, the changes which complexation produces in the P—P couplings are compared with changes produced in the analogous phosphine complexes.The synthesis and characterization of Ph2P(E)[(CH2)2P(E)Ph]2(CH2)2P(E)Ph2 (E = S or Se) and (Se)P[(CH2)2P(Se)Ph2]3 are reported. The 31P nmr spectra of these compounds are compared with those of the parent tetraphosphines and other members of the corresponding tetraoxide–tetrachalcogenide series.

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283. The preparation of di- and tri-tertiary phosphines

Abstract: Convenient preparative routes to sodium diphenylphosphide and lithium diethylphosphide are described. Reaction of these phosphides with aliphatic polychloro-compounds allows ready preparation of bi-and tri-dentate tertiary phosphines.

Cited by 253 publications

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2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

Nuclear magnetic resonance studies of the solvation of phosphorus(V) selenides, 1,2-bis(diphenylphosphino)ethane, and tris(dimethylamino)phosphine telluride by sulfur dioxide

A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

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283. The preparation of di- and tri-tertiary phosphines

Abstract: Convenient preparative routes to sodium diphenylphosphide and lithium diethylphosphide are described. Reaction of these phosphides with aliphatic polychloro-compounds allows ready preparation of bi-and tri-dentate tertiary phosphines.

Cited by 253 publications

References 0 publications

2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

2-Oxacyclopentylidene, 2-Oxacyclohexylidene, and 2-Oxacycloheptylidene Rhenium Complexes by Reaction of ω-Alkynols with the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary

Nuclear magnetic resonance studies of the solvation of phosphorus(V) selenides, 1,2-bis(diphenylphosphino)ethane, and tris(dimethylamino)phosphine telluride by sulfur dioxide

A 31P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the 31P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

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A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides