Mills David P, Cooper Oliver J, McMaster Jonathan, Lewis William, Liddle Stephen T
School of Chemistry, University of Nottingham, University Park, Nottingham, UKNG7 2RD.
Dalton Trans. 2009 Jun 21(23):4547-55. doi: 10.1039/b902079a. Epub 2009 Apr 24.
Reaction of [YI(3)(THF)(3.5)] with three equivalents of [KBz] (Bz = CH(2)C(6)H(5)) affords the tri-benzyl complex [Y(Bz)(3)(THF)(3)] () in excellent yield. Complex reacts with H(2)C(PPh(2)NSiMe(3))(2) (H(2)BIPM) to afford the yttrium-alkyl-carbene complex [Y(BIPM)(Bz)(THF)] (, BIPM = {C(PPh(2)NSiMe(3))(2)}). Compound reacts with one equivalent of benzophenone to give the alkoxy 1,2-migratory insertion product [Y(BIPM)(OCPh(2)Bz)(THF)] () rather than the alkene Wittig-product Ph(2)C[double bond, length as m-dash]C(PPh(2)NSiMe(3))(2). Reaction of with one or more equivalents of benzophenone does not afford any detectable alkene products, rather it apparently catalyses rearrangement of monomeric to afford dimeric [{Y(micro-BIPM)(OCPh(2)Bz)}(2)] (). Investigations reveal that formation of is proportional to the amount of benzophenone added, but the benzophenone is recovered at the end of the reaction. Reaction of with diphenyldiazene affords the 1,2-migratory insertion product [Y(BIPM){N(Ph)N(Ph)(Bz)}(THF)] () Compounds , , , , and have been variously characterised by X-ray crystallography, multi-nuclear NMR spectroscopy, FTIR spectroscopy, and CHN micro-analyses. Density functional theory calculations on reveal the HOMO to be localised at the Y-C(alkyl) bond which is commensurate with the observed reactivity.
[YI₃(THF)₃.₅]与三当量的[KBz]（Bz = CH₂C₆H₅）反应，以优异的产率得到三苄基配合物[Y(Bz)₃(THF)₃]（ ）。该配合物与H₂C(PPh₂NSiMe₃)₂（H₂BIPM）反应，得到钇-烷基-卡宾配合物[Y(BIPM)(Bz)(THF)]（ ，BIPM = {C(PPh₂NSiMe₃)₂}）。化合物 与一当量的二苯甲酮反应，得到烷氧基1,2-迁移插入产物[Y(BIPM)(OCPh₂Bz)(THF)]（ ），而不是烯烃维蒂希产物Ph₂C═C(PPh₂NSiMe₃)₂。 与一当量或更多当量的二苯甲酮反应，未得到任何可检测到的烯烃产物，相反，它显然催化单体重排，得到二聚体[{Y(μ-BIPM)(OCPh₂Bz)}₂]（ ）。研究表明， 的形成与加入的二苯甲酮量成正比，但反应结束时二苯甲酮被回收。 与二苯基二氮烯反应，得到1,2-迁移插入产物[Y(BIPM){N(Ph)N(Ph)(Bz)}(THF)]（ ）。化合物 、 、 、 和 已通过X射线晶体学、多核NMR光谱、FTIR光谱和CHN微量分析等多种方法进行了表征。对 的密度泛函理论计算表明，最高占据分子轨道（HOMO）定域在Y-C(烷基)键上，这与观察到的反应活性相符。
