Ylidylphosphorsulfide, ‐selenide, ‐disulfide, ‐sulfidselenide und ‐diselenide

Jochem, Georg; Karaghiosoff, Konstantin; Plank, Stefan; Schmidpeter, Stefan Dick Und Alfred

doi:10.1002/cber.19951281212

Cited by 41 publications

(8 citation statements)

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“…reported the synthesis of four‐membered phosphorus–chalcogen (RPE) 2 heterocycles (E=S, Se); subsequent reactions with N‐heterocyclic carbenes (NHCs) resulted in base‐stabilized phosphinidene sulfides. Schmidpeter and co‐workers prepared stable monomeric phosphorous monochalcogenides without bulky or intramolecularly coordinating substituents, which are stabilized through conjugation with a triphenylphosphoniumylidyl moiety (therefore named ylidylphosphorchalcogenides) and large contributions of zwitterionic resonance structures. Product studies suggested the transient generation of phosphinidene chalcogenides (thermally or photochemically) from various precursors, such as phospholene, phosphirane, or phosphanorbornadiene chalcogenides, and starting materials containing four‐membered rings with a P 2 E 2 core (E=S, Se) …”

Section: Methodsmentioning

confidence: 99%

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

2020

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The structures and reactivities of organic phosphinidene chalcogenides have been mainly inferred from trapping or complexation experiments. Phosphinidene chalcogenide derivatives appear to be an elusive family of molecules that have been suggested as reactive intermediates in multiple organophosphorus reactions. The quest to isolate “free” phosphinidene chalcogenides remains a challenge in the field. Here, we present the synthesis, IR, and UV/Vis spectroscopic identification of hitherto elusive phenylphosphinidene oxide and phenylphosphinidene sulfide from the corresponding phosphonic diazide precursors. We isolated these higher congeners of nitroso‐ and thionitrosobenzene in argon matrices at 10 K. The spectral assignments are supported by B3LYP/6–311++G(3df,3pd) and MP2/cc‐pVTZ computations.

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Section: Methodsmentioning

confidence: 99%

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

2020

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“…The halides X−PS (X = F, Cl, or Br) have been studied by various spectroscopies in the gas phase, and for ClPS a PS distance of 1.86 Å and a ClPS angle of 110° was calculated. , In addition, thioxophosphanes and selenoxophosphane of formula Ar−PS or Ar−PSe (Ar = −C 6 H 2 -6-NMe 2 -2,4-t-Bu 2 ) have been characterized spectroscopically in solution . More recently, several ylidylphosphorus sulfides and selenides of formula Ph 3 P(R)C−PE (R = Me, Et, Ph, 3-MeC 6 H 4 , 2,6-Cl 2 C 6 H 3 , SiMe 3 ) have been characterized . However, these differ in the sense that stabilization is achieved by a major contribution from a zwitterionic resonance form (b) as depicted by A structural determination of Ph 3 PC(Et)PSe showed that it displayed a short C−P(Se) bond of 1.702(6) Å and a long P−Se distance of 2.129(2) Å (cf.…”

Section: Compounds Of Formula Re=e‘ (E = Group 15 E‘ = Group 16 Element)mentioning

confidence: 99%

π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements

1999

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ContentsI. Introduction 3463 II. Multiple Bonding Models 3466 III. Lone Pair Character versus Multiple Bonding 3468 IV. Doubly Bonded Compounds 3469 A. Compounds of Formula RE)ER (E ) Group 13 Element) 3469 B. Compounds of Formula RE)E′R 2 (E ) Group 13, E′ ) Group 14 Element) 3470 C. Dianions of Formula [R 2 E)ER 2 ] 2-(E ) Group 13 Element) 3470 D. Monoanions of Formula [R 2 E)E′R 2 ] -(E ) Group 13; E′ ) Group 14 Element) 3472 E. Compounds of Formula R 2 E−E ¨′R 2 (E ) Group 13; E′ ) Group 15 Element) 3472 F. Compounds of Formula R 2 E−E′R and [R 2 E−E′] -(E ) Group 13, E′ ) Group 16 Element) 3475 G. Compounds of Formula R 2 E)ER 2 and [RE ¨)E ¨R] 2-(E ) Group 14 Element) 3477 H. Compounds of Formula R 2 E)E ¨′R (E ) Group 14, E′ ) Group 15 Element) 3481 I. Compounds of Formula [R 2 E)E′R 2 ] + (E ) Group 14; E′ ) Group 15 Element) 3484 J. Compounds of Formula R 2 E)E′: (E ) Group 14; E′ ) Group 16 Element) 3485 K. Compounds of Formula RE ¨)E ¨R (E or E′ ) N, P, As, Sb, or Bi) 3486 L. Compounds of Formula RE)E′ (E ) Group 15, E′ ) Group 16 Element) 3489 V. Compounds with Formal Bond Order >2 and Triply Bonded Compounds 3490 A. Range of Compounds 3490 B. Compounds with Potential Triple Bonding to a Group 13 Element 3491 C. Compounds with Potential Triple Bonding to a Group 14 Element 3493 D. Compounds with Triple Bonding between Group 14 and 15 Elements 3494 E. Compounds with Triple Bonding between Group 15 Elements 3495 VI. Conclusions 3495 VII. Acknowledgments 3496 VIII. References 3496Philip Power received his B.A. degree from Trinity College Dublin in 1974 and his D.Phil. degree, under the supervision of M. F. Lappert, from the University of Sussex in 1977. After postdoctoral studies with R. H. Holm at Stanford, he joined the faculty at the University of California, Davis, where he is currently Professor of Chemistry. His main research interests involve the structural chemistry of organoalkali metal and organocopper compounds, low-coordinate transition metal chemistry, multiple bonding in main group chemistry, and the development of new ligands for the stabilization of low coordination numbers, unusual oxidation states, and multiple bonding in both transition metal and heavier main group compounds. He is a recipient of fellowships from the A. P. Sloan and Alexander von Humboldt foundations. In addition he has been Reilly Lecturer at the University of Notre Dame (1995), Faculty Research Lecturer at the University of Iowa (1993), and the

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“…Its stability is rationalized by a high contribution of the zwitterionic resonance formula 2b (path II). 2 Aiming at the synthesis of new cationic phosphorus species, we are investigating reactions of imidazoliumyl-substituted P-centered cations such as [L (R,R0) PCl 2 ] + 3 + (L R,Me = imidazolium-2-yl, R = Aryl, Alkyl; R 0 = H, Me, Cl) 3 towards substitution 3,4 (e.g. 4 + ,5 + ), coordination, 5 oxidation 6 or reduction 7 (e.g.…”

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confidence: 99%

Tetra-cationic imidazoliumyl-substituted phosphorus–sulfur heterocycles from a cationic organophosphorus sulfide

et al. 2016

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The reaction of imidazoliumyl-substituted P((III)) cations of type [L((R,Me))PCl2](+) (3a,b(+); L(R,Me) = imidazolium-2-yl a: R = Me; b: R = iPr) with (Me3Si)2S leads to the formation of tetra-cationic, eight-membered phosphorus sulfur heterocycles [L((R,Me))PS]4(4+) (9a,b(4+)), which can be explained by the tetramerization of the intermediately formed cationic phosphorus monosulfide [L((R,Me))PS](+) (8a,b(+)). The P4S4 ring adopts a crown conformation as observed for cyclo-S8. The Lewis base DMAP (4-dimethylaminopyridine) initiates a deoligomerization- and dismutation reaction of 9a,b(4+) to give P((I)) centered cation [L((R,Me))2P](+) (12a,b(+)) and phosphorus disulfide [(DMAP)2PS2](+) (14(+)).

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Ylidylphosphorsulfide, ‐selenide, ‐disulfide, ‐sulfidselenide und ‐diselenide

Cited by 41 publications

References 58 publications

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements

Tetra-cationic imidazoliumyl-substituted phosphorus–sulfur heterocycles from a cationic organophosphorus sulfide

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Ylidylphosphorsulfide, ‐selenide, ‐disulfide, ‐sulfidselenide und ‐diselenide

Cited by 41 publications

References 58 publications

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C6H5P=O and C6H5P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C6H5P=O and C6H5P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements

Tetra-cationic imidazoliumyl-substituted phosphorus–sulfur heterocycles from a cationic organophosphorus sulfide

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Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C₆H₅P=O and C₆H₅P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene