Synthese und Struktur von η1-Phosphaallyl-, η1-Arsaallylund η1-Stibaallyleisen-Komplexen [(η5-C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P, As, Sb)

Abstract

Inhaltsu È bersicht. Bei der Umsetzung a Èquimolarer Mengen an [(g 5 -C 5 Me 5 )(CO) 2 FeE(SiMe 3 ) 2 ] (1 a: E = P; 1 b: As; 1 c: Sb) mit Diphenylketen werden die g 1 -Phosphaallyl-, g 1 -Arsaallylund g 1 -Stibaallylkomplexe [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )-C(OSiMe 3 )=CPh 2 ] (2 a: E = P; 2 b: As; 2 c: Sb) erhalten. Die Moleku È lstukturen von 2 b und 2 c wurden durch Ro È ntgenstrukturanalysen ermittelt.Syntheses and Structures of g 1 -Phosphaallyl, g 1 -Arsaallyl, and g 1 -Stibaallyl Iron Complexes [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )C(OSiMe 3 )=CPh 2 ] (E = P, As, Sb)Abstract. The reaction of equimolar amounts of [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 ) 2 ] (1 a: E = P; 1 b: As; 1 c: Sb) and diphenylketene afforded the g 1 -phosphaallyl-, g 1 -arsaallyl-, and g 1 -stibaallyl complexes [(g 5 -C 5 Me 5 )(CO) 2 Fe±E(SiMe 3 )-C(OSiMe 3 )=CPh 2 ] (2 a: E = P; 2 b: As; 2 c: Sb). The molecu-lar structures of 2 b and 2 c were elucidated by single crystal X-ray analyses.

Synthesis and Reactivity of Bidentate N‐Heterocyclic Carbene‐Phosphinidene Supported Si(IV) Dicationic Complexes

“…Additionally, LIFDI‐MS measurement shows the mass for [ 2 a +2 eq Ph 2 CCO] 2+ . Similar reactivity is observed by Appel as well as by Weber and coworkers [38–39] . Treatment of PhP(SiMe 3 ) 2 with an equimolar amount of diphenylketene afforded the adduct Ph(Me 3 Si)P−C(OSiMe 3 )=CPh 2 .…”

“…To investigate the thermal stability as well as the reactivity of [38][39] Treatment of PhP(SiMe 3 ) 2 with an equimolar amount of diphenylketene afforded the adduct Ph(Me 3 Si)PÀ C(OSiMe 3 )=CPh 2 . The same reactivity was observed for [Fe]À P(SiMe 3 ) 2 .…”

Phosphaalkenes with Inverse Electron Density

“…Delocalization of the negative charge into the CϭO bond is clear by its elongation from 1.240(2) Å (as measured in 22b) [49] Di-tert-butylaluminium chloride reacted smoothly with equimolar amounts of 22a or 22b in toluene at Ϫ30 C°to yield the adducts 60a,b as extremely moisture-sensitive orange solids. Attempts to grow crystals of 60a and 60b from C 6 D 6 solutions at 6 C over a period of 3 weeks led to the formation of crystals of the dismutation products 61a and 61b instead.…”