In search of α-eliminations of carbon induced by sixteen electron iron: photolysis and thermolysis of derivatives of phenyl substituted cyclobutanes and cyclopropanes
作者:Rhonda L. Trace、W.M. Jones
DOI:10.1016/0022-328x(89)88078-7
日期:1989.10
Photolysis of dicarbonyl(η5-cyclopentadienyl)(1-phenylcyclobutane-1-carbonyl)iron is proposed to give the hydride complex Ph(cyclobutenyl)Fe(Cp)-(CO)H which dissociates to 1-phenylcyclobutene and FpH (Fp = η5-cyclopentadienyldicarbonyliron). The FpH complex can oxidatively add to the sixteen electron acyl or σ complexes (Ph(cyclobutyl)-C(O)FeCp(CO) and Ph(cyclobutyl)FeCp(CO) respectively) to produce
(CNO-NR(2) = the coordinated semicarbazone ligand). Another group of semicarbazones (viz. salicylaldehyde semicarbazone, 2-hydroxyacetophenone semicarbazone, and 2-hydroxynaphthaldehyde semicarbazone) has also been observed to undergo a similar chemical transformation upon reaction with [Rh(PPh(3))(3)Cl] under similar experimental conditions as before, and these transformed semicarbazones bind to rhodium as
在三烷基胺和二烷基胺(NR(2)R'; R = Et,(i)Pr,( n)Bu; R'= H或R'= R)通过C-NH(2)键解离并形成新的C-NR(2)键(其中NR(2)片段由胺提供) )。转化的半脲配体以铑的C,N,O供体形式与铑结合,从而提供[Rh(PPh(3))(2)(CNO-NR(2))Cl](CNO-NR(2) =配位的半脲配体)。在相似的实验下,与[Rh(PPh(3))(3)Cl]发生反应后,还观察到另一组半咔唑酮(即水杨醛半卡巴,、 2-羟基苯乙酮半卡巴zone和2-羟基萘醛半卡巴zone)经历了相似的化学转化。像以前一样 并且这些转化的半咔唑酮以二价阴离子O,N,O供体的形式与铑结合,从而提供[Rh(PPh(3))(2)(ONO(n)-NR(2))Cl](ONO(n) -NR(2)=配位的半脲配体; n = 1-3)。[Rh(PPh(3))(2)(CNO-NEt(2))C