Selective P-C-Bond Cleavage in P(III)-Triphenylmethyl Compounds

Plack, Volker; Goerlich, Jens R.; Schmutzler, Reinhard

doi:10.1002/(sici)1521-3749(1998120)624:12<1940::aid-zaac1940>3.0.co;2-o

Cited by 7 publications

(2 citation statements)

References 7 publications

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“…Grützmacher recognized the synthetic potential for low-coordinate phosphorus compounds and reported on the synthesis and reactivity of C -tritylphosphaalkyne . It was again Schmutzler who found that trityl can serve as a leaving group, but in this case only preliminary work was done; recent computational studies stressed the reactivity-determining key role of P -trityl groups in three-membered phosphorus heterocycles . To date, only few coordination compounds of P -trityl substituted phosphane complexes have been reported .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

et al. 2012

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P-Trityl substituted Li/Cl phosphinidenoid tungsten(0) complex (OC)5W{Ph3CP(Li/12-crown-4)Cl} (3) was prepared via chlorine/lithium exchange in complex (OC)5W{Ph3CPCl2} (2) using (t)BuLi in the presence of 12-crown-4 in tetrahydrofuran (THF) at low temperature; complex 3 possesses significantly increased thermal stability in contrast to previously reported analogue derivatives. Terminal phosphinidene-like reactivity of 3 was used in reactions with benzaldehyde and isopropyl alcohol as oxaphosphirane complex (OC)5W{Ph3CPC(Ph)O} (5) and phosphinite complex (OC)5W{Ph3CP(H)O(i)Pr} (6) were obtained selectively. Reaction of 3 with phosgene allowed to obtain the first kinetically stabilized chloroformylphosphane complex (OC)5W{Ph3CP(Cl)C(O)Cl} (4). Density functional theory (DFT) calculations revealed remarkable differences in the degree of P-Li bond dissociation 3a-d: using a continuum model 3 displays a covalent character of P-Li bond (COSMO (THF)) (a), which becomes elongated if 12-crown-4 is coordinated to lithium (b) and is cleaved if a dimethylether unit is additionally coordinated to lithium (c). A similar result was obtained for the case of 3(thf)4 in which also a solvent-separated ion pair structure is present (d). All products were unambiguously characterized by various spectroscopic means and, in the case of 2 and 4-6, by single-crystal X-ray diffraction analysis. In all structures very long P-C bonds were determined being in the range from 1.896 to 1.955 Å.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

et al. 2012

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“…6 In a preliminary study Schmutzler showed that trityl can serve as a leaving group if such phosphane derivatives are treated with very strong acids. 7 On the other hand, we recently demonstrated that the accessibility of transition-metal oxaphosphirane complexes was hugely facilitated due to the availability of Li/Cl phosphinidenoid complexes. 8 Of particular importance was the first derivative bearing the sterically demanding trityl group at phosphorus, 8d being stable at ambient temperature for some hours.…”

Section: Introductionmentioning

confidence: 99%

CPh₃ as a functional group in P-heterocyclic chemistry: elimination of HCPh₃ in the reaction of P-CPh₃ substituted Li/Cl phosphinidenoid complexes with Ph₂CO

et al. 2016

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P-CPh3 substituted oxaphosphirane complexes 3 were prepared using Li/Cl phosphinidenoid complexes 2 (M = Cr, Mo, W) and benzaldehyde. Employing 2 and benzophenone resulted in the formation of oxaphospholane complexes 4 and 5, the former bearing a benzo[c]-1,2-oxaphospholane and the latter a novel pentacyclic P-ligand. According to DFT studies the latter P-heterocycle arises from formal dimerization of a transient benzofused 2-phosphafurane complex 8, one of the fragments undergoing water-catalyzed [1,3]H shift (4) and the other (11) formed via elimination of HCPh3.

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Dehydroiodierung von Iod‐ und Diiodmethan durch einen transienten Phosphinidenkomplex

et al. 2007

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Selective P-C-Bond Cleavage in P(III)-Triphenylmethyl Compounds

Cited by 7 publications

References 7 publications

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

CPh₃ as a functional group in P-heterocyclic chemistry: elimination of HCPh₃ in the reaction of P-CPh₃ substituted Li/Cl phosphinidenoid complexes with Ph₂CO

Dehydroiodierung von Iod‐ und Diiodmethan durch einen transienten Phosphinidenkomplex

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Selective P-C-Bond Cleavage in P(III)-Triphenylmethyl Compounds

Cited by 7 publications

References 7 publications

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

Synthesis and Reactions of the First Room Temperature Stable Li/Cl Phosphinidenoid Complex

CPh3 as a functional group in P-heterocyclic chemistry: elimination of HCPh3 in the reaction of P-CPh3 substituted Li/Cl phosphinidenoid complexes with Ph2CO

Dehydroiodierung von Iod‐ und Diiodmethan durch einen transienten Phosphinidenkomplex

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CPh₃ as a functional group in P-heterocyclic chemistry: elimination of HCPh₃ in the reaction of P-CPh₃ substituted Li/Cl phosphinidenoid complexes with Ph₂CO