Reactivity of Ferriophosphaalkene [(η5-C5Me5)(CO)2Fe–P=C(NMe2)2] and Ferrioarsaalkene [(η5-C5Me5)(CO)2Fe–As=C(NMe2)2] Towards Trimethylaluminium, -gallium and -indium

Abstract

Reaction of equimolar amounts of the ferriophosphaalkene [(η5‐C5Me5)(CO)2FeP=C(NMe2)2] (1a) or the ferrioarsaalkene [(η5‐C5Me5)(CO)2FeAs=C(NMe2)2] (1b) with trimethylaluminium, trimethylgallium and trimethylindium afforded the adducts [(η5‐C5Me5)(CO)2FeE{MMe3}C(NMe2)2] with E = P; M = Al (2a), Ga (3a), In (4a) and E = As; M = Al (2b), Ga (3b), and In (4b). These compounds feature η1‐coordination of the phosphaalkene or the arsaalkene ligand towards the Lewis acid via the pnictogen atom. The molecular structures of 2a and 3a were elucidated by X‐ray diffraction analyses.

N-Heterocyclic Carbene Adducts of Main Group Elements and Their Use as Ligands in Transition Metal Chemistry

“…It should be noted, however, that related arsaalkenes were studied by Weber already since 1996, 628 and for instance, the acyclic . 629 The reactivity of this "metalloarsaalkene" was further studied toward carbonylmetal complexes, 630,631 and trimethylaluminum, -gallium, and -indium, 632 and its alkylation, protonation, and silylation produced a series of cationic complexes of the type [(η 5 -C 5 Me 5 )Fe(CO) 2 {RAsC(NMe 2 ) 2 }] (R = Me, H, SiMe 3 ). 561 In 519) through reduction with potassium graphite (Scheme 127).…”

“…It should be noted, however, that related arsaalkenes were studied by Weber already since 1996, and for instance, the acyclic diaminocarbene–arsinidene adduct [{(Me 2 N) 2 C}­AsSiMe 3 ] was used for the preparation of the iron­(II) complex [(η 5 -C 5 Me 5 )­Fe­(CO) 2 {AsC­(NMe 2 ) 2 }] . The reactivity of this “metalloarsaalkene” was further studied toward carbonylmetal complexes, , and trimethylaluminum, -gallium, and -indium, and its alkylation, protonation, and silylation produced a series of cationic complexes of the type [(η 5 -C 5 Me 5 )­Fe­(CO) 2 {RAsC­(NMe 2 ) 2 }] (R = Me, H, SiMe 3 ) . In 1997, the first N-heterocyclic carbene–arsinidene adducts [(IMes)­AsR] ( 518a , R = Ph; 518b , R = C 6 F 5 ) were isolated by Arduengo from the reaction of IMes with hexaphenylcyclo­hexaarsane, (AsPh) 6 , or tetrakis­(pentafluorophenyl)­cyclotetraarsane, (AsC 6 F 5 ) 4 , respectively (Scheme ).…”

Overview of the Synthesis and Catalytic Reactivity of Transition Metal Complexes Based on C═P Bond Systems

“…104 Next, the synthesis 105 were created. 106 An iron(I) complex was obtained after oneelectron reduction of [FeBr 2 (BPEP)] by KC 8 , MesMgBr, or Mes 2 Mg(THF) 2 . 107,108 Another example (104A-C) involved one-electron reductions of 103 in reactions with π-acid ligands (L = CO, RNC), TEMPO, and homolytic elimination of Mes* from a highly congested phosphorus atom.…”

“…Metallophosphaalkenes [Cp(CO) 2 Fe–PC(OSiMe 3 )R] (R = Mes, Ph, or t Bu) were obtained in reaction of iron disilylphosphane and with acid chlorides . Next, the synthesis and reactivity of another complex [(η 5 -C 5 Me 5 )(CO) 2 FePC(NMe 2 ) 2 ] was demonstrated toward Me 3 Al, Me 3 In and Me 3 Ga, and three corresponding complexes [(η 5 -C 5 Me 5 )(CO) 2 FeP{MMe 3 }C(NMe 2 ) 2 ] (M = Al, In, Ga) were created . An iron(I) complex was obtained after one-electron reduction of [FeBr 2 (BPEP)] by KC 8 , MesMgBr, or Mes 2 Mg(THF) 2 . , Another example ( 104A-C ) involved one-electron reductions of 103 in reactions with π-acid ligands (L = CO, RNC), TEMPO, and homolytic elimination of Mes* from a highly congested phosphorus atom.…”