Structure and dissociation of ylidyl chlorophosphanes

Jochem, Georg; Breitsameter, Florian; Schier, Annette; Schmidpeter, Alfred

doi:10.1002/(sici)1098-1071(199608)7:4<239::aid-hc5>3.3.co;2-j

Cited by 3 publications

(4 citation statements)

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“…3,5,7-Trichloro-2,6,8-tris(triphenylphosphoranediyl)-4-triphenylphosphonio-1,3,5,7-tetraarsabarrelane tetrachloroarsenate(iii) (13): AsCl 3 (0.25 mL, 2.90 mmol) was added to a stirred solution of 3 (1.22 g, 2.90 mmol) in [39] 216.1(4) [40] (tBuNECl) 2 209.6(7) [41] 224.9(3) [42] 211.4 (7) 225.2(2) Ph 3 PC(ECl 2 ) 2 208.6(2) [2] 221.3(1) 209.3 (2) 222.2(1) 210.0 (2) 225.2(1) 211.6 (2) 227.4(1) (CH 2 ) 3 (MeN) 2 ECl ± 235.7(2) [43] Ph 3 PMeCECl 2 209.6(2) [2] 221.6(1) 218.7 (2) 237.0(1) (CH 2 ) 2 (tBuN) 2 ECl 231.4(1) [44] 237.5(2) [45] (CH 2 ) 2 (MeN) 2 ECl ± 239.0(5) [43] E(Ph 3 PCECl) 3 CPPh 3 235.3(2) [4] 247.4(2) 247.8(2) 251.6(2) pyridine (8 mL) at 60 8C. After 3 h the solution had turned red and was kept at 60 8C for additional 18 h without stirring.…”

Section: Methodsmentioning

confidence: 99%

Acyclic, Ring, and Cage As,C Compounds from Trimethylsilyl Ylides and AsCl3

Breitsameter¹,

Schmidpeter²,

Nöth³

2000

Chem. Eur. J.

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From the reaction of trimethylsilyl ylides with AsCl3 the dichloroarsanyl ylides 2b and 5b are obtained. As shown by X-ray structure determination, their AsCl2 groups deviate systematically from the symmetric orientation. This conformation enables an effective charge transfer from the ylide moiety to one of the As-Cl bonds, which as a consequence is up to 15 pm longer than the other. At the same time the length of the As-C bonds in 2b and 5b indicates a partial double bond. The effects observed here are of the same type as those observed for the corresponding dichlorophosphanyl ylides; they are, however, more pronounced. The 1:1 condensation of the bis(trimethylsilyl) ylide 3 and AsCl3 yields the oligomers (Ph3PCAsCl)2,3,4. The dimer 7b has a diarsetane structure. HCl adds readily to one of its As-C bonds without opening it. The trimer and the tetramer are ionic. The cation of the trimer forms a six-membered ring with a delocalized arsenium/phosphonium charge, the cation of the tetramer forms a barrelane cage with a phosphonio substituent, and the anion is AsCl4- in both cases (10, 13). An arsa-phosphocyanine cation as in 10 is also part of the diphosphonio isoarsindolide tetrachloroarsenate(III) 12. The structures of 7b.HCl, 10, and 13 reflect again an ylide to As-Cl charge transfer. The As-Cl bonds of 13 are by far the longest ones known for a chloroarsine (average 249 pm).

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Section: Methodsmentioning

confidence: 99%

Acyclic, Ring, and Cage As,C Compounds from Trimethylsilyl Ylides and AsCl3

Breitsameter¹,

Schmidpeter²,

Nöth³

2000

Chem. Eur. J.

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“…Abb Die Darstellungen der eingesetzten Ylidylchlorphosphane [1,12], und des Bis(diphenylphosphanyl)-methanids und -amids [13,14] …”

Section: Das Chlormethylchlorphosphan Lc [4] Reagiertunclassified

“…Triphenylphosphoniumylid-substituierte Chlorphosphane und Dichlorphosphane (wie 1 und 2) zeichnen sich durch eine begünstigte PCl-Dissoziation aus [1,2], schließen sich aber in ihren Reak tionen ansonsten den geläufigen Chlorphosphanen an [3]. So lassen sie sich durch Kondensation mit Trimethylsilylphosphanen in ylidsubstituierte Diund Triphosphanderivate überführen.…”

Section: Introductionunclassified

Die Kondensation von Ylidylchlorphosphanen mit Phosphanen und Bis(diphenylphosphanyl)methan und -amin / The Condensation of Ylidyl Chlorophosphines with Phosphines and Bis(diphenylphosphino)methane and -amine

Breitsameter

Mayer

Schmidpeter

2000

Zeitschrift Für Naturforschung B

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Ylidyl chlorophosphanes 1 and dichlorophosphanes 2 react with trimethylsilyl phosphanes to yield the ylidyl diphosphanes 3, 4,5, 7 and the 2-ylidyl triphosphanes 8. From the reaction of compounds 1 with lithium diphosphanyl amide and diphosphanyl methanide result the ylidyl diphosphonium ylides 11 and ylidyl diphosphinimines 13. The former rearrange to give the ylidyl triphosphanyl methanes 12. The chloromethyl diphosphinimine 13c enters a cyclization to give the 1,2,3,5-azatriphosphole derivative 14, the structure of which has been solved by X-ray analysis. From the reaction of ylidyl bis(chlorophosphanes) 17 and 20 with the same reagents the 1,2,4,5-tetraphosphinine derivative 18 and the 1,2,3,5,6-azatetraphosphinine derivatives 19 and 21 are obtained.

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“…3 [2, 3] setzen w ir U n tersu c h u n g en an C hlo rp h o sp h an y l-y lid en (Y lid y l-c h lo rp h o sp h a n e n ) [4] fort. D ie g em isc h t su b stitu ie rte V erbindung 3 läßt sich in b ew ä h rter W eise aus dem B is(trim eth y lsily l)y lid [Ph3P C (S iM e 3)2] und D ich lo rp h e n y lp h o sp h a n über die b eo b a ch tb are Z w isc h e n stu fe 1 h in w eg d arste l len u n d e rm ö g lic h t ein en S tru k tu rv e rg leic h m it den vierfach g le ic h su b stitu ie rte n V erbindungen 2 [5] und 4 [1], Ihre R ed u k tio n fü h rt zu m D ip h o sp h an 8 und 1,2 ,4 ,5 -T etra p h o sp h in a n 9, d ie sich fü r einen w eiteren S tru k tu rv e rg leic h an b ieten .…”

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