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An Ylide‐Substituted Tetraphosphene, Cyclotetraphosphane, and Bicyclotetraphosphane
Author(s) -
Schrödel HausPeter,
Nöth Heinrich,
SchmidtAmelunxen Martin,
Schoeller Wolfgang W.,
Schmidpeter Alfred
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301215
Subject(s) - chemistry , ylide , trimethylsilyl , coupling constant , crystallography , stereochemistry , medicinal chemistry , double bond , computational chemistry , polymer chemistry , physics , particle physics
The reaction of two specific ylidyl dichlorophosphanes, Ph3P=CR‐PCl 2 , with P(SiMe 3 ) 3 yields the ylidyl trimethylsilyl diphosphenes Ph 3 P=CR.P=P‐SiMe 3 as primary products which form two different types of dimers: the cyclotetraphosphane 9 (R = SiMe 3 ), and the tetraphosphene 10 (R = 2,6‐Cl, 2,/C 6 H 3 ). The latter compound is readily converted to the bis(ylidyl)biocyclotetraphosphane 11 . The molecular structures of 9 and 11 allow a strong transanular interaction between teh ylide‐substituted phosphorus atoms, which results in very large two‐bond coupling constants ( 2J pp = 184 and 332 Hz respectively). The central P bond in 11 is relatively long (220.7 pm); quantum chemical calculations show the lengthening to be a consequence of the perpendicular orientation of the ylidic donor p‐orbital.