Shutov Pavel L, Karlov Sergey S, Harms Klaus, Tyurin Daniil A, Churakov Andrei V, Lorberth Jörg, Zaitseva Galina S
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35032 Marburg/Lahn, Germany.
Inorg Chem. 2002 Nov 18;41(23):6147-52. doi: 10.1021/ic0257423.
Syntheses of title compounds, viz. N(CH2CH2NR)3E (1, E = Sb, R = Me; 4, E = Bi, R = Me; 6, E = Sb, R = SiMe3; 8, E = Bi, R = SiMe3), by the reaction of E(NAlk2)3 (3, E = Sb, Alk = Et; 5, E = Bi, Alk = Me) with N(CH2CH2NMeH)3 (2) or N(CH2CH2NSiMe3H)3 (7) are reported. The reactions of SbCl3 with N[CH2CH2N(Me)Li]3 or N[CH2CH2N(SiMe3)Li]3 and BiCl3 with N[CH2CH2N(SiMe3)Li]3 resulted in compounds 1, 6, and 8, respectively. Composition and structures of all novel compounds were established by 1H and 13C NMR spectroscopy and mass spectrometry. The X-ray structural study of 8 clearly indicated the presence of transannular interaction BiNdat in this compound, while 6 possesses a long Sb...Ndat distance. The structural data obtained from geometry optimizations on 6 and 8 reproduce experimental trends, i.e., a decrease in the E-Ndat distance from Sb to Bi. The values of electron density in E-Ndat critical point and the Laplacian of charge density for 8 indicate that a closed-shell interaction exists between the metal atom and Ndat atom.
报道了通过E(NAlk2)3（3，E = Sb，Alk = Et；5，E = Bi，Alk = Me）与N(CH2CH2NMeH)3（2）或N(CH2CH2NSiMe3H)3（7）反应合成标题化合物，即N(CH2CH2NR)3E（1，E = Sb，R = Me；4，E = Bi，R = Me；6，E = Sb，R = SiMe3；8，E = Bi，R = SiMe3）。SbCl3与N[CH2CH2N(Me)Li]3或N[CH2CH2N(SiMe3)Li]3的反应以及BiCl3与N[CH2CH2N(SiMe3)Li]3的反应分别得到化合物1、6和8。通过1H和13C NMR光谱以及质谱确定了所有新化合物的组成和结构。对8的X射线结构研究清楚地表明该化合物中存在跨环相互作用BiNdat，而6具有较长的Sb...Ndat距离。从对6和8的几何优化获得的结构数据再现了实验趋势，即从Sb到Bi的E-Ndat距离减小。8的E-Ndat临界点处的电子密度值和电荷密度的拉普拉斯值表明金属原子和Ndat原子之间存在闭壳相互作用。
