Verbindungen des Typs (F3C)2EE′R mit Pseudohalogen-Charakter (E = P, As; E′ = S, Se, Te)

Grobe, J.; Vetter, J.

doi:10.1002/(sici)1521-3749(199912)625:12<2085::aid-zaac2085>3.0.co;2-s

Cited by 3 publications

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References 7 publications

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“…Starting from the racemic diphosphetane 4 , bisphosphanes 6a – d were synthesized by reaction with the respective diaryl dichalcogenides. These so-called dismutation reactions have already been studied in detail between noncyclic diphosphanes and diorganyl dichalcogenides …”

Section: Resultsmentioning

confidence: 99%

C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

et al. 2016

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Racemic carborane-based bisphosphanes were obtained by dismutation reactions between a carborane-based diphosphetane and diaryl dichalogenides. NMR spectroscopic and theoretical studies revealed a two-step mechanism explaining the high stereoselectivity of these reactions. The coordination chemistry of the multidentate P,N ligands 6c and 6d in copper(I) and silver(I) complexes was studied. While 6d acted exclusively as tetradentate ligand, 6c showed either tridentate or tetradentate coordination depending on the metal and the counterion.

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Section: Resultsmentioning

confidence: 99%

C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

et al. 2016

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“…The first step in the addition of two chalcogen atoms to 3 could occur either via (a) insertion of a chalcogen atom into the two P–P bonds to give the eight-membered ring 7 or (b) oxidation of the three-coordinate phosphorus atoms to four-coordinate centers with retention of the six-membered ring, as in 9 . There is literature precedent for the insertion of sulfur of selenium into the P–P bonds of diphosphanes R 2 P–PR 2 . Although the treatment of 1,4-(CH 2 ) 2 (P i Pr) 4 with sulfur has been reported to oxidize all four three-coordinate phosphorus centers to give 9 (with t Bu groups replaced by i Pr), there is no structural evidence for this product, and the characterization data are very limited …”

Section: Resultsmentioning

confidence: 99%

Chalcogenation of the 1,4-C₂P₄ Ring: Oxidation, Isomerization, Insertion, and Ring Contraction

Elder

Chivers

2013

Inorg. Chem.

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The reaction of H2C(PCl2)2 with 4 equiv of (t)BuMgCl in tetrahydrofuran (THF) produces 1,4-(CH2)2(P(t)Bu)4, 1, in about 65% yield. This six-membered ring reacts directly with elemental sulfur or selenium in toluene at low temperatures to give the mono- and dichalcogenides 1,4-(CH2)2(P(t)BuE)(P(t)Bu)3 (E = S, 2a, E = Se, 2b) and 1,4-(CH2)2-2,5-(P(t)BuE)2(P(t)Bu)2 (E = S, 3a, E = Se, 3b). X-ray structural determinations showed that 3a and 3b are isostructural in the solid state; the six-membered C2P4 ring exhibits a twist-boat geometry with chalcogen substituents in syn positions in each case. Density functional theory (DFT) calculations for the three possible isomers of disubstitution were performed to elucidate the factors that favor the 2,5-isomer. Thermal isomerism was observed in solutions of 3b or 3a in toluene at 60 and 95 °C, respectively, to give the corresponding 2,6-isomers. With an excess of chalcogen in toluene at reflux, the four-membered rings (H2C)(P(t)BuE)2E (E = S, 4a, E = Se, 4b) were obtained and identified by multinuclear NMR spectroscopy and single crystal X-ray crystallography, which showed the (t)Bu groups in a trans orientation with respect to the CP2E ring. With a large excess of chalcogen, the five-membered rings (H2C)(P(t)BuE)2E2 (E = S, 5a, E = Se, 5b) were also observed; the X-ray structure of 5b revealed a half-envelope conformation for the CP2Se2 ring. The direct reaction of 4a with sulfur in boiling toluene does not produce 5a, whereas 5b is formed slowly and in low yields from 4b and selenium under similar conditions. On the basis of DFT calculations of the relative energies of likely intermediates, chalcogen insertion into the P-P bonds of 3a and 3b to give eight-membered C2P4E2 rings, followed by monomerization, is proposed as a feasible pathway for the formation of the four-membered CP2E heterocycles 4a and 4b.

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Alkyl Chalcogenides: Selenium- and Tellurium-based Functional Groups

Kataoka

Watanabe

2005

Comprehensive Organic Functional Group Transformations II

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Verbindungen des Typs (F3C)2EE′R mit Pseudohalogen-Charakter (E = P, As; E′ = S, Se, Te)

Cited by 3 publications

References 7 publications

C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

Chalcogenation of the 1,4-C₂P₄ Ring: Oxidation, Isomerization, Insertion, and Ring Contraction

Alkyl Chalcogenides: Selenium- and Tellurium-based Functional Groups

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Verbindungen des Typs (F3C)2EE′R mit Pseudohalogen-Charakter (E = P, As; E′ = S, Se, Te)

Cited by 3 publications

References 7 publications

C2-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

C2-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

Chalcogenation of the 1,4-C2P4 Ring: Oxidation, Isomerization, Insertion, and Ring Contraction

Alkyl Chalcogenides: Selenium- and Tellurium-based Functional Groups

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C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

C₂-Symmetric P,N Ligands Derived from Carborane-Based Diphosphetanes: Synthesis and Coordination Chemistry

Chalcogenation of the 1,4-C₂P₄ Ring: Oxidation, Isomerization, Insertion, and Ring Contraction