School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
Inorg Chem. 2011 Oct 3;50(19):9631-41. doi: 10.1021/ic201372a. Epub 2011 Aug 31.
Treatment of the complex [U(Tren(TMS))(Cl)(THF)] [1, Tren(TMS) = N(CH(2)CH(2)NSiMe(3))(3)] with Me(3)SiI at room temperature afforded known crystalline [U(Tren(TMS))(I)(THF)] (2), which is reported as a new polymorph. Sublimation of 2 at 160 °C and 10(-6) mmHg afforded the solvent-free dimer complex [{U(Tren(TMS))(μ-I)}(2)] (3), which crystallizes in two polymorphic forms. During routine preparations of 1, an additional complex identified as [U(Cl)(5)(THF)][Li(THF)(4)] (4) was isolated in very low yield due to the presence of a slight excess of [U(Cl)(4)(THF)(3)] in one batch. Reaction of 1 with one equivalent of lithium dicyclohexylamide or bis(trimethylsilyl)amide gave the corresponding amide complexes [U(Tren(TMS))(NR(2))] (5, R = cyclohexyl; 6, R = trimethylsilyl), which both afforded the cationic, separated ion pair complex [U(Tren(TMS))(THF)(2)][BPh(4)] (7) following treatment of the respective amides with Et(3)NH·BPh(4). The analogous reaction of 5 with Et(3)NH·BAr(f)(4) [Ar(f) = C(6)H(3)-3,5-(CF(3))(2)] afforded, following addition of 1 to give a crystallizable compound, the cationic, separated ion pair complex [{U(Tren(TMS))(THF)}(2)(μ-Cl)][BAr(f)(4)] (8). Reaction of 7 with K[Mn(CO)(5)] or 5 or 6 with [HMn(CO)(5)] in THF afforded [U(Tren(TMS))(THF)(μ-OC)Mn(CO)(4)] (9); when these reactions were repeated in the presence of 1,2-dimethoxyethane (DME), the separated ion pair [U(Tren(TMS))(DME)][Mn(CO)(5)] (10) was isolated instead. Reaction of 5 with [HMn(CO)(5)] in toluene afforded [{U(Tren(TMS))(μ-OC)(2)Mn(CO)(3)}(2)] (11). Similarly, reaction of the cyclometalated complex [U{N(CH(2)CH(2)NSiMe(2)Bu(t))(2)(CH(2)CH(2)NSiMeBu(t)CH(2))}] with [HMn(CO)(5)] gave [{U(Tren(DMSB))(μ-OC)(2)Mn(CO)(3)}(2)] [12, Tren(DMSB) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)]. Attempts to prepare the manganocene derivative [U(Tren(TMS))MnCp(2)] from 7 and K[MnCp(2)] were unsuccessful and resulted in formation of [{U(Tren(TMS))}(2)(μ-O)] (13) and [MnCp(2)]. Complexes 3-13 have been characterized by X-ray crystallography, (1)H NMR spectroscopy, FTIR spectroscopy, Evans method magnetic moment, and CHN microanalyses.
用 Me(3)SiI 在室温下处理 [U(Tren(TMS))(Cl)(THF)] [1，Tren(TMS) = N(CH(2)CH(2)NSiMe(3))(3)]，得到已知的结晶 [U(Tren(TMS))(I)(THF)] (2)，它被报道为一种新的多晶型物。在 160°C 和 10(-6)mmHg 的条件下升华 2 得到无溶剂二聚体配合物 [{U(Tren(TMS))(μ-I)}(2)] (3)，它结晶为两种多晶型物。在 1 的常规制备过程中，由于一批中存在稍过量的 [U(Cl)(4)(THF)(3)]，因此分离出另一种复合物 [U(Cl)(5)(THF)][Li(THF)(4)] (4)，其产率非常低。1 与 1 当量的二环己基锂酰胺或双(三甲基硅基)酰胺反应，得到相应的酰胺配合物 [U(Tren(TMS))(NR(2))] (5，R = 环己基；6，R = 三甲基硅基)，它们都在各自的酰胺与 Et(3)NH·BPh(4)反应后得到阳离子、分离的离子对配合物 [U(Tren(TMS))(THF)(2)][BPh(4)] (7)。类似地，5 与 Et(3)NH·BAr(f)(4) [Ar(f) = C(6)H(3)-3,5-(CF(3))(2)]的反应，在加入 1 得到可结晶的化合物后，得到阳离子、分离的离子对配合物 [{U(Tren(TMS))(THF)}(2)(μ-Cl)][BAr(f)(4)] (8)。7 与 K[Mn(CO)(5)]或 5 或 6 与 [HMn(CO)(5)]在 THF 中的反应得到 [U(Tren(TMS))(THF)(μ-OC)Mn(CO)(4)] (9)；当这些反应在 1,2-二甲氧基乙烷 (DME) 的存在下重复进行时，分离的离子对 [U(Tren(TMS))(DME)][Mn(CO)(5)] (10)被分离出来。5 与 [HMn(CO)(5)]在甲苯中的反应得到 [{U(Tren(TMS))(μ-OC)(2)Mn(CO)(3)}(2)] (11)。同样，环金属化配合物 [U{N(CH(2)CH(2)NSiMe(2)Bu(t))(2)(CH(2)CH(2)NSiMeBu(t)CH(2))}]与 [HMn(CO)(5)]的反应得到 [{U(Tren(DMSB))(μ-OC)(2)Mn(CO)(3)}(2)] [12，Tren(DMSB) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)]。从 7 和 K[MnCp(2)]制备茂金属衍生物 [U(Tren(TMS))MnCp(2)]的尝试均未成功，导致形成 [{U(Tren(TMS))}(2)(μ-O)] (13)和 [MnCp(2)]。配合物 3-13 已通过 X 射线晶体学、(1)H NMR 光谱、FTIR 光谱、Evans 方法磁矩和 CHN 微量分析进行了表征。
