Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes
作者:Benedict M. Gardner、Gábor Balázs、Manfred Scheer、Floriana Tuna、Eric J. L. McInnes、Jonathan McMaster、William Lewis、Alexander J. Blake、Stephen T. Liddle
DOI:10.1002/anie.201400798
日期:2014.4.22
(1; TrenTIPS=NCH2CH2NSi(iPr)3}3) with NaPH2 afforded the novel f‐block terminal parent phosphide complex [U(TrenTIPS)(PH2)] (2; U–P=2.883(2) Å). Treatment of 2 with one equivalent of KCH2C6H5 and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded the unprecedented metal‐stabilized terminal parent phosphinidenecomplex [U(TrenTIPS)(PH)][K(B15C5)2] (4; UP=2.613(2) Å). DFT calculations reveal
The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium(<scp>iv</scp>) and uranium(<scp>iv</scp>) alkyls
作者:Benedict M. Gardner、Peter A. Cleaves、Christos E. Kefalidis、Jian Fang、Laurent Maron、William Lewis、Alexander J. Blake、Stephen T. Liddle
DOI:10.1039/c4sc00182f
日期:——
thorium(IV) and uranium(IV) alkyls. Reaction of KCH2Ph with [U(TrenTIPS)(I)] [2a, TrenTIPS = N(CH2CH2NSiPri3)33−] gave the cyclometallate [UN(CH2CH2NSiPri3)2(CH2CH2NSiPri2C[H]MeCH2)}] (3a) with the intermediate benzyl complex not observable. In contrast, when [Th(TrenTIPS)(I)] (2b) was treated with KCH2Ph, [Th(TrenTIPS)(CH2Ph)] (4) was isolated; which is notable as Tren N-silylalkyl metalalkyls tend
我们报告了5f轨道参与在三酰胺胺th(IV)和铀(IV)烷基的σ键易位反应趋势中的意外反转中的作用。KCH 2 Ph与[U(Tren TIPS)(I)] [ 2a,Tren TIPS = N(CH 2 CH 2 NSiPr i 3)3 3-的反应]得到环金属盐[U N(CH 2 CH 2 NSiPr i 3)2(CH 2 CH 2 NSiPr i 2 C [H] MeCH 2)}](3a)的中间苄基配合物是不可观察到的。相反,当用KCH 2 Ph处理[Th(Tren TIPS)(I)](2b)时,分离出[Th(Tren TIPS)(CH 2 Ph)](4)。这是值得注意的,因为Tren N-甲硅烷基烷基金属烷基倾向于自发地环金属化。热解4个中cyclometallate的甲苯和形成的挤出结果[钍N(CH 2 CH 2 NSiPr我3)2(CH 2 CH 2 NSiPr我2 C [H]机