Synthesis and borane coordination of primary alkenyl- and alkynylphosphines

Shay, R. H.; Diel, Bruce N.; Schubert, David M.; Norman, A. D.

doi:10.1021/ic00286a031

Cited by 17 publications

(23 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Twenty years ago, a pioneering work of Norman et al described the synthesis of some functionalized derivatives, the primary allylic and propargylic phosphine-boranes. 9 A low kinetic stability was observed for these unsaturated species. Recently, the vinylphosphine-borane has been synthesized.…”

Section: Introductionmentioning

confidence: 98%

Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane

et al. 2009

View full text Add to dashboard Cite

Ethynyl- and allenylphosphine-boranes have been prepared by addition at low temperature of borane on the free phosphine. Purification was performed by selective trapping in vacuo and the complexes were characterized by NMR and infrared spectroscopy and mass spectrometry. A kinetic stability lower than that of the corresponding free systems was observed. A series composed of these compounds and methyl-, vinyl-, allyl- and propargylphosphine-boranes was investigated by photoelectron spectroscopy and B3LYP/aug-cc-pVTZ quantum chemical study in order to define the variation in the electronic effects between the free systems and the corresponding complexes. Although the complexation only led to minor changes in the unsaturated moiety, the P-C bond shortens in all cases because of the charge transfer from phosphorus to boron. Similar rotamers can be found in the complexes and the free systems, and the order of the relative stability is reversed only in the case of the allenyl derivative. The calculated complexation energies are between 80-100 kJ mol(-1) in agreement with flash vacuum thermolysis experiments. The photoelectron spectra can be easily described in the case of alpha,beta-unsaturated compounds by the change of the direct conjugation between the lone electron pair and the pi-bond in the free phosphines to hyperconjugation of the sigma(P-B) bond with the unsaturated moiety in the corresponding complexed derivatives. In the case of beta,gamma-unsaturated derivatives the observed hyperconjugation in phosphines disappears on complexation.

show abstract

Section: Introductionmentioning

confidence: 98%

Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane

et al. 2009

View full text Add to dashboard Cite

show abstract

“…The unsaturated carbon centres are also heavily deshielded (δ c 137.4 ( J PC 19.0 Hz) C 1 ; 209.9 ( J PC 11.3 Hz) C 2 ), the latter in particular being more characteristic of an allenic, 40 rather than alkynic centre; indeed, these data are in good agreement with those for the limited range of phosphinoallenes § ( Table 2) described previously. 14,41 We thus confidently formulate 15 as (Et 2 N) 2 PC-(Ph)vCvCH 2 (Scheme 2).…”

Section: Formation Of a Phosphino-allenementioning

confidence: 92%

“…Yield: 0.800 g (4 : 1 8 : SnBu 4 ). NMR (C 6 D 6 , 30°C): (14). In a manner similar to that described for 8, using HP(SiMe 3 ) 2 (1.04 g, 5.84 × 10 −3 mol), n BuLi (2.5 M, 2.3 cm 3 , 5.75 × 10 −3 mol) and 3 (1.25 g, 6.00 × 10 −3 mol).…”

Section: General Methodsmentioning

confidence: 99%

“…The primary propargyl phosphane H 2 PCH 2 CuCH has also been reported. 14 This lack of activity is surprising given continued interest in developing polyfunctional phosphorus-containing molecules, driven by their utility as ligands, optoelectronically active π-conjugates 15 and, topically, frustrated Lewis pairs (FLPs). 16 In these contexts, propargylphosphanes should constitute ideal 'building-block' substrates, and allow for incorporation of further functionality (e.g.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of 3-stannyl and 3-silyl propargyl phosphanes and the formation of a phosphinoallene

Saunders

Crossley

2016

Dalton Trans.

View full text Add to dashboard Cite

The group 14 chloropropargyls R3EC ≡ CCH2Cl (R3E = (n)Bu3Sn, Ph3Sn, Me2PhSi, (i)Pr3Si, (n)Pr3Si, (n)Bu3Si), obtained by a modified literature procedure, react with LiPPh2 to afford the novel propargyl phosphanes Ph2PCH2C ≡ CER3 in high yield, as viscous oils; (Me3Si)2PCH2C ≡ CSiPhMe2 is similarly obtained from LiP(SiMe3)2. In contrast, the reaction of PhC[triple bond, length as m-dash]CCH2MgCl with ClP(NEt2)2 fails to produce a comparable propargyl phosphane, but generates preferentially (>70%) the novel phosphinoallene (Et2N)2PC(Ph) = C = CH2, which is characterised spectroscopically, and through its reaction with HCl. The coordination chemistry of representative phosphanes is explored with respect to platinum and palladium for the first time.

show abstract

“…[2][3][4][5][6] The length of the P-B bonds has been predicted by theoretical calculations 7 and determined by microwave spectroscopy. 12 Some nondistillable kinetically stable tungsten complexes of simple unsaturated phosphines have also been described. 10,11 For instance, such systems are significantly more acidic in the gas phase than the corresponding saturated analogs.…”

Section: Introductionmentioning

confidence: 99%

Vinylphosphine-borane: Synthesis, gas phase infrared spectroscopy, and quantum chemical vibrational calculations

Khater

Guillemin

Bénidar

et al. 2008

The Journal of Chemical Physics

View full text Add to dashboard Cite

Both experimental and theoretical investigations are reported on the infrared spectrum of vinylphosphine-borane (CH(2)=CHPH(2) x BH(3)), a donor-acceptor complex. The gas phase infrared spectra (3500-600 cm(-1)) have been recorded at 0.5 cm(-1) resolution. This first primary alpha,beta-unsaturated phosphine-borane synthesized up to now is kinetically very unstable in the gas phase and decomposes rapidly into two fragments: the free vinylphosphine CH(2)=CHPH(2) and the monoborane BH(3) which dimerizes to form the more stable diborane B(2)H(6). Spectra of free CH(2)=CHPH(2) and B(2)H(6) compounds were also recorded to assign some vibration modes of the complex in very dense spectral regions. The analysis was completed by carrying out quantum mechanical calculations by density functional theory method at the B3LYP/6-31+G(**) level. Anharmonic frequencies and infrared intensities of the two predicted gauche and syn conformers of the vinylphosphine-borane complex were calculated in the 3500-100 cm(-1) region with the use of a variational approach, implemented in the P_ANHAR_V1.2 code. Because of the relatively weak interaction between the vinylphosphine and the monoborane, the vibrations of the complex can easily be subdivided into modes localized in the CH(2)=CHPH(2) and BH(3) moieties and into "intermolecular" modes. Localized modes are unambiguously correlated with the modes of the isolated monomers. Therefore, they are described in terms of the monomer vibrations, and the complexation shifts are defined as Delta nu = nu(complex) - nu(monomer) to make the effect of the complexation precise on each localized mode. In this objective, anharmonic frequencies and infrared intensities of the BH(3) monomer and the stable gauche and syn conformers of the free vinylphosphine were obtained at the same level of theory. In the gas phase, only the syn form of the complex was observed and assigned. All theoretically predicted frequencies and complexation shifts in magnitude and direction are in good agreement with experiment. By infrared spectroscopy assisted by quantum chemical calculations, the consequences of the complexation of an alpha,beta-unsaturated phosphine by borane on the physicochemical properties of the formed 12-atom complex have been efficiently evaluated.

show abstract

Synthesis and borane coordination of primary alkenyl- and alkynylphosphines

Cited by 17 publications

References 3 publications

Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane

Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane

Synthesis of 3-stannyl and 3-silyl propargyl phosphanes and the formation of a phosphinoallene

Vinylphosphine-borane: Synthesis, gas phase infrared spectroscopy, and quantum chemical vibrational calculations

Contact Info

Product

Resources

About