Dalton Transactions p. 19473 - 19484 (2016)
Update date:2022-08-17
Topics:
Gowda, Vasantha
Laitinen, Risto S.
Telkki, Ville-Veikko
Larsson, Anna-Carin
Antzutkin, Oleg N.
Lantto, Perttu
The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13C and 15N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P21/n. Both 13C and 15N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13C and 15N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.
View MoreAnyang Double Circle Auxiliary CO.,LTD
Contact:0086-134 6082 4403
Address:dongfeng road, anyang city, henan province,china
Contact:+86+21-58956006 15800617331
Address:402 Room, 150# Cailun Road, Zhangjiang high tech park, Shanghai
Taizhou Elitechemie MediPharma Technology Co.,Ltd.
Contact:+86-523-86810021
Address:Building G14,NO.1 Avenue,China Medical City, Taizhou, Jiangsu,China
Changyi Xinxing Technology Development Co., Ltd.
Contact:0086-510-86651065(Time Zone:8),86651656
Address:94 Yingbinxilu WestRoad, Huangtu Town, Jiangyin City, Jiangsu, China
Jiangxi Province Bethel Pharmaceutical Co., Ltd.
Contact:+86-795-259 3456 ,+86-15957688008 13566650571
Address:Huangjindui Chemical Park, Shanggao County ,Yichun city,Jiangxi Province
Doi:10.1007/BF01524961
()Doi:10.1016/j.cattod.2019.10.009
(2020)Doi:10.1016/j.tet.2006.04.077
(2006)Doi:10.1021/ic051083t
(2006)Doi:10.1021/acs.joc.5b02894
(2016)Doi:10.1016/0031-9422(92)80382-O
(1992)