Schurko RW, Wasylishen RE, Phillips AD
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3, Canada.
J Magn Reson. 1998 Aug;133(2):388-94. doi: 10.1006/jmre.1998.1460.
Solid-state 27Al NMR spectra have been obtained for a crystalline 1:1 complex of AlCl3 and OPCl3. Aluminum chloride phosphoryl chloride, AlCl3 . OPCl3 (1), is unusual in that the Al-O-P bond angle is close to 180 degrees. From analysis of the 27Al MAS NMR spectra, it was determined that the 27Al nuclear quadrupole coupling constant is 6.0(1) MHz, the asymmetry in the electric field gradient (efg) tensor is 0.15(2), and the isotropic chemical shift, deltaiso(27Al), is 88(1) ppm. Solid-state 27Al NMR of a stationary sample reveals a line shape affected by a combination of anisotropic chemical shielding and second-order quadrupolar interactions. Analysis of this spectrum yields a chemical shift anisotropy of 60(1) ppm and orientations of the chemical shift and electric field gradient tensors in the molecular frame. Experimental results are compared with those calculated using ab initio Hartree-Fock and density functional theory. Copyright 1998 Academic Press.
已获得AlCl₃与OPCl₃的晶体1:1配合物的固态²⁷Al NMR谱。氯化铝磷酰氯，AlCl₃·OPCl₃(1)，不同寻常之处在于Al - O - P键角接近180度。通过对²⁷Al MAS NMR谱的分析，确定²⁷Al核四极耦合常数为6.0(1) MHz，电场梯度(efg)张量的不对称性为0.15(2)，各向同性化学位移δiso(²⁷Al)为88(1) ppm。静态样品的固态²⁷Al NMR显示出线形受各向异性化学屏蔽和二阶四极相互作用组合的影响。对该谱的分析得出化学位移各向异性为60(1) ppm以及化学位移和电场梯度张量在分子框架中的取向。将实验结果与使用从头算Hartree - Fock和密度泛函理论计算的结果进行了比较。版权所有1998年学术出版社。
