Karhu Aino J, Pakkanen Olli J, Rautiainen J Mikko, Oilunkaniemi Raija, Chivers Tristram, Laitinen Risto S
Laboratory of Inorganic Chemistry, Center for Molecular Materials, University of Oulu, P.O. Box 3000, Oulu FI-90014, Finland.
Department of Chemistry, University of Calgary, 2500 University Drive, N.W., Calgary, Alberta T2N 1N4, Canada.
Dalton Trans. 2016 Apr 14;45(14):6210-21. doi: 10.1039/c5dt04236d.
The third member of the series of imidoselenium(II) chlorides ClSe[N(tBu)Se]nCl (n = 3) (9) has been isolated from the cyclocondensation reaction of tBuNH2 and SeCl2 in THF in a molar ratio of ca. 3:1 and characterized in the form of two polymorphs 9a and 9b by single crystal X-ray analysis. The unusual structural features of this nine-atom chain are explained satisfactorily in terms of a bonding model that invokes intra-molecular secondary bonding interactions and hyperconjugation. The reaction of the bifunctional reagent ClSe[N(tBu)Se]2Cl (8) with tBuNH2 in THF occurs via concurrent pathways to give 1,3,5-Se3(NtBu)3 (1) and 1,3-Se3(NtBu)2 (3a). The energetics of the reactions of tBuNH2 and SeCl2 in THF have been calculated at the PBE0/def2-TZVPP level of theory in order to assess the feasibility of ClSe[N(tBu)Se]nCl (7–9, n = 1–3) as intermediates in the formation of known cyclic selenium imides. DFT calculations were also employed to explore the energy profile of the pathway of the formation of the first member of the series ClSeN(tBu)SeCl (7) from tBuNH2 and SeCl2 in THF at 298 K. The neutral ligand ClSeN(tBu)SeCl (7) is Se,Se′-coordinated to the metal centre in the unusual adduct [PdCl2{Se,Se′-(SeCl)2N(tBu)}]·[PdCl2{Se,Se′-Se4(NtBu)3}]·MeCN (10·MeCN), which is the first metal complex of an imidoselenium(II) chloride.
亚氨基硒（II）氯化物系列的第三个成员ClSe[N(tBu)Se]nCl（n = 3）（9）是通过叔丁胺（tBuNH2）与二氯化硒（SeCl2）在四氢呋喃（THF）中以约3:1的摩尔比进行环缩合反应分离得到的，并通过单晶X射线分析以两种多晶型物9a和9b的形式进行了表征。这条九原子链的异常结构特征通过一个涉及分子内二次键相互作用和超共轭的键合模型得到了令人满意的解释。双功能试剂ClSe[N(tBu)Se]2Cl（8）与tBuNH2在THF中的反应通过并行途径进行，生成1,3,5 - Se3(NtBu)3（1）和1,3 - Se3(NtBu)2（3a）。为了评估ClSe[N(tBu)Se]nCl（7 - 9，n = 1 - 3）作为已知环状硒酰亚胺形成中间体的可行性，在PBE0/def2 - TZVPP理论水平上计算了tBuNH2与SeCl2在THF中的反应能量学。还采用密度泛函理论（DFT）计算来探索在298 K下，tBuNH2与SeCl2在THF中形成该系列第一个成员ClSeN(tBu)SeCl（7）的反应途径的能量分布。中性配体ClSeN(tBu)SeCl（7）在异常加合物[PdCl2{Se,Se′-(SeCl)2N(tBu)}]·[PdCl2{Se,Se′-Se4(NtBu)3}]·MeCN（10·MeCN）中以Se,Se′配位到金属中心，这是第一个亚氨基硒（II）氯化物的金属配合物。
