一氧化碳加到[PtCl(R)(NN)](R =烃基; NN =螯合N,N-配体)上,得到中性五坐标[PtCl(R)(CO)(NN)]或阳离子四-坐标[Pt(R)(CO)(NN)] +配合物,具体取决于N,N-配体的空间拥挤。对于R-芳基,在温和条件下进行迁移插入过程,并获得相应的酰基物质。报道了五配位加合物与亲核试剂的一些反应,并描述了金属上的取代或配位一氧化碳的添加。
Cationic platinum(II) - or palladium(II)-carbyl complexes and unsaturated substrates: a facile way to C-C bond formation
作者:Vicenzo De Felice、Maria E. Cucciolito、Augusto De Renzi、Francesco Ruffo、Diego Tesauro
DOI:10.1016/0022-328x(94)05294-l
日期:1995.5
η3 coordination, except in the reaction of alkenes with Pd(II) complexes. In this case, a free R-substituted alkene is produced via a relatively fast β-elimination process from a Pd-alkyl intermediate. Different regiochemistries are detected in the reaction between monosubstituted olefins (propene or styrene) and homologous Pt and Pd complexes. The Pt-C bond is always formed with the terminal unsubstituted
烯烃,炔烃,1,2-和1,3-二烯与[MR(NN)(MeCN)] +(M = Pt或Pd; R =烃基; N = N =二齿氮配体)反应生成R-取代的衍生物。将有机片段通常在η保持在金属环境中1或η 3协调,除在用Pd烯烃的反应(II)复合体。在这种情况下,通过相对快速的β-消除过程由Pd-烷基中间体产生游离的R-取代的烯烃。在单取代的烯烃(丙烯或苯乙烯)与同源的Pt和Pd络合物之间的反应中检测到不同的区域化学。Pt-C键始终与末端未取代的烯烃碳形成,而对于内部碳,尤其是在被Pd物种观察到被苯基取代的情况下,尤其倾向于内部碳。中性[MClR(NN)]的反应性明显较低。在这种情况下,当M = Pt时,不饱和有机底物通常会添加到金属中,从而提供相当稳定的tbp五配位络合物。
Nucleophilic Attack of Carbanions on Cationic Platinum(II) Nitrile Complexes Affording Stable η1-Imine Enol and η1-Enamine Coordinated Fragments
作者:Maria E. Cucciolito、Vincenzo De Felice、Federico Giordano、Ida Orabona、Francesco Ruffo
Cationicnitrileplatinum(II) complexes of formula [PtMe(RCN)(bipy)]+ undergo nucleophilic addition of carbanions −CH(COX)(COY) (X, Y= Me, OMe), −CH(CO2Me)CN and −CH(CN)2 to afford neutral products. According to the nature of the nucleophile, the organic ligand fragment displays either an imino enol or an enamine isomeric structure. The Pt−N bond can be cleaved upon reaction with acids with formation