Reactivity of Phosphaalkenes toward Carbene Complexes

Reaction of phosphaalkenes RP=C(NMe 2 ) 2 (R = t -Bu, Me 3 Si), featuring an inverse distribution of electron density about the P--C double bond, with Fischer carbene complexes [(CO) 5 M=C(OEt)Ar] (Ar=Ph, 2-MeC 6 H 4 , 2-MeOC 6 H 4 , M = Cr, W) afforded a mixture of complexes [(CO) 5 M{P(R)=C(NMe 2 ) 2 }] and [(CO) 5 M{P(R)=C(OEt)Ar}]. The treatment of phosphaalkene HP=C(NMe 2 ) 2 with compound [(CO) 5 W=C(OEt)(2-MeOC 6 H 4 )] gives rise to the formation of an ( E / Z )-mixture of [(CO) 5 W{P(CH(NMe 2 ) 2 )=C(OEt)(2-MeOC 6 H 4 )}].     

Metallsubstituierte Phosphaalkene und Acylphosphane. 31. Zur Reaktivität von (η5-C5Me5)(CO)2FeP = C(NMe2)2 gegenüber Zinndichlorid. Röntgenstrukturanalyse von {(η5-C5Me5)[η1-(Me2N)2C = P?P = C(NMe2)2](CO)2Fe}+{[Me2N)2C]2P}+(FeCl4)2−

Transition-Metal Substituted Phosphaalkenes and Acyl Phosphanes. 31 [1] Reactivity of (η⁵-C₅Me₅)(CO)₂FeP = C(NMe₂)₂ towards Tin Dichloride. X-Ray Structure Analysis of {(η⁵-C₅Me₅)[η¹-(Me₂N)₂C = P? P = C(NMe₂)₂](CO)₂Fe}⁺{[Me₂N)₂C]₂P}⁺(FeCl₄)^2? Reaction of metallophosphaalkene (η⁵-C₅Me₅)(CO)₂ · FeP = C(NMe₂)₂ ( 1 ) with anhydrous tin dichloride affords the salt-like compound {(η⁵-C₅Me₅)[η¹-(Me₂N)₂C = P? P = C(NMe₂)₂] · (CO)₂Fe}⁺{[(Me₂N)₂C]₂P}⁺(FeCl₄)^2? 5 which is characterized by single crystal X-ray analysis and spectra (IR, ¹H, ³¹P-NMR).