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From Disilene (SiSi) to Phosphasilene (SiP) and Phosphacumulene (PCN)
Author(s) -
Willmes Philipp,
Cowley Michael J.,
Hartmann Marco,
Zimmer Michael,
Huch Volker,
Scheschkewitz David
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201308525
Subject(s) - steric effects , substituent , chemistry , yield (engineering) , alkene , crystallography , alkyl , stereochemistry , medicinal chemistry , materials science , organic chemistry , catalysis , metallurgy
The generation of heavier double‐bond systems without by‐ or side‐product formation is of considerable importance for their application in synthesis. Peripheral functional groups in such alkene homologues are promising in this regard owing to their inherent mobility. Depending on the steric demand of the N‐alkyl substituent R, the reaction of disilenide Ar 2 SiSi(Ar)Li (Ar=2,4,6‐ i Pr 3 C 6 H 2 ) with ClP(NR 2 ) 2 either affords the phosphinodisilene Ar 2 SiSi(Ar)P(NR 2 ) 2 (for R= i Pr) or P‐amino functionalized phosphasilenes Ar 2 (R 2 N)SiSi(Ar)P(NR 2 ) (for R=Et, Me) by 1,3‐migration of one of the amino groups. In case of R=Me, upon addition of one equivalent of tert ‐butylisonitrile a second amino group shift occurs to yield the 1‐aza‐3‐phosphaallene Ar 2 (R 2 N)SiSi(NR 2 )(Ar)PCN t Bu with pronounced ylidic character. All new compounds were fully characterized by multinuclear NMR spectroscopy as well as single‐crystal X‐ray diffraction and DFT calculations in selected cases.