Kinetic and Mechanistic Investigation of Metallacycle Ring Opening in an Ortho-Metalated Lutetium Aryl Complex
Kinetic and Mechanistic Investigation of Metallacycle Ring Opening in an Ortho-Metalated Lutetium Aryl Complex
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邻位金属化镥芳基配合物中金属环开环的动力学和机理研究
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发表时间：
2011
期刊：
影响因子：
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通讯作者：
Paul G. Hayes
中科院分区：
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作者：
Kevin R. D. Johnson;Paul G. Hayes
本文报道了邻位金属化双（膦亚胺）咔唑配合物（LPh-κ 3 N，κ2CP-Ph）Lu（THF）（1a）和（LPipp-κ 3 N，κ2CP-Ph）Lu（THF）（1b; L = [1，8-（Ph_2P_（NAr）_2dmc]; Ar = Ph（LPh），p-isopropylphenyl（LPipp）; dmc = 3，6-dimethylcarbazolide）的开环反应。1a，B与大体积苯胺（2，4，6-三甲基苯胺，MesNH 2; 2，4，6-三异丙基苯胺，TripNH 2）反应促进两个邻位金属化的对苯基的金属配位开环，释放出双（苯胺）产物（LPh-κ 3 N）Lu（NHMes）2（2）和（LPipp-κ 3 N）Lu（NHTrip）2（3）。无论使用的TripNH 2或MesNH 2的量如何，双环开环总是占优势以得到双（苯胺）产物，而不是单（苯胺）。与此相反，配合物1b与体积较大的试剂2，4，6-三叔丁基苯胺（Mes* NH 2）的反应仅引起一个邻位金属化的对苯基的金属杂环开环，仅得到单（苯胺）配合物（LPipp-κ 3 N，κCP-Ph）Lu（NHMes*）（4）。复合体4迅速经历了一个鼹鼠内...
Reactivity involving metallacycle ring opening of ortho-metalated bis(phosphinimine)carbazolide complexes (LPh-κ3N,κ2CP-Ph)Lu(THF) (1a) and (LPipp-κ3N,κ2CP-Ph)Lu(THF) (1b); L = [1,8-(Ph2P═NAr)2dmc]; Ar = Ph (LPh), p-isopropylphenyl (LPipp); dmc = 3,6-dimethylcarbazolide) is described. Reaction of 1a,b with bulky anilines (2,4,6-trimethylaniline, MesNH2; 2,4,6-triisopropylaniline, TripNH2) promoted metallacycle ring opening of two ortho-metalated P-phenyl groups to liberate the bis(anilide) products (LPh-κ3N)Lu(NHMes)2 (2) and (LPipp-κ3N)Lu(NHTrip)2 (3). Regardless of the quantity of TripNH2 or MesNH2 utilized, double ring opening always prevailed to afford the bis(anilide) product, rather than the mono(anilide). In contrast, reaction of complex 1b with the bulkier reagent 2,4,6-tri-tert-butylaniline (Mes*NH2) only caused metallacycle ring opening of one ortho-metalated P-phenyl group, affording the mono(anilide) complex (LPipp-κ3N,κCP-Ph)Lu(NHMes*) (4) exclusively. Complex 4 rapidly undergoes an intramole...