Experimental and theoretical study of^(13)C shielding tensors in new-style molybdenum complex  

作　　者：HOU Guangjin1,2, WANG Liying2, LU Xiaoming3, ZHENG Anmin2, DENG Feng2 &YE Chaohui1,2 1. Department of Physics, Huazhong University of Science and Technology, Wuhan 430074, China 2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chi-nese Academy of Sciences, Wuhan 430071, China 3. Department of Chemistry, Capital Normal University, Beijing 100037, China 

出　　处：《Science China Chemistry》2004年第3期214-221,共8页中国科学（化学英文版）

摘　　要：13C 2D-PASS spectra of two new cis-dioxo catecholatomolybdenum complexes (NH2CH2NH2CHCH2)2(H+)3[MovO 2(C6H4O2)2] and (NH2CH2CH2CH2NH2)2(H+)3[Mo(v)O2 (C2H2O2)2] have been obtained by solid-state nuclear magnetic resonance (NMR), in which the spinning sidebands were well-separated. The principal components of the 13C shielding tensors were extracted by theoretically fitting the intensities of 13C spinning sidebands. The effects of counter cations on 13C chemical shift isotropy and shielding tensor of cis-dioxo catecholatomolybdenum complex anion [Mo (v)O2(C6H4O2)2]3? were studied, comparing the 13C CSA of those carbon sites in complex anions with that of the counter cations. Based on the known structure of the molybdenum complex crystal, theoretical values of 13C shielding tensors were calculated by the ainitio GIAO method, in comparison with the experimental results.C 2D-PASS spectra of two new cis-dioxo catecholatomolybdenum complexes (NH2CH2NH2CHCH3)2 (H+)3 [Mo(v)O2(C6H4O2)2] and (NH2CH2CH2CH2NH2)2(H+)3[Mo(v)O2(C6H4O2)2] have been obtained by solid-state nuclear magnetic resonance (NMR), in which the spinning sidebands were well-separated. The principal components of the 13C shielding tensors were ex-tracted by theoretically fitting the intensities of 13C spinning sidebands. The effects of counter cations on 13C chemical shift isotropy and shielding tensor of cis-dioxo catecholatomolybdenum complex anion [Mo(v)O2(C6H4O2)2]3- were studied, comparing the 13C CAS of those carbon sites in complex anions with that of the counter cations. Based on the dnown structure of the molyb-denum complex crystal, theoretical values of 13C shielding tensors were calculated by the ab initio GIAO method, in comparison with the experimental results.

关 键 词：NMR  MAGIC angle spinning  chemical SHIFT anisotropy  SHIELDING tensor  cis-dioxo-monomolybdenum. 

分 类 号：O614[理学—无机化学]