Synthesis, Characterization, and Theoretical Studies of Group 4 Amido Hydrotris(pyrazolyl)borate Complexes

• Published in: Inorganic chemistry Vol. 42; no. 9; pp. 3008 - 3015
• Main Authors: Cai, Hu, Lam, Wai Han, Yu, Xianghua, Liu, Xiaozhan, Wu, Zhong-Zhi, Chen, Tianniu, Lin, Zhenyang, Chen, Xue-Tai, You, Xiao-Zeng, Xue, Ziling
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05.05.2003
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic026063v

Titanium and zirconium amido complexes containing a hydrotris(pyrazolyl)borate (Tp) or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand TpM(NMe2)3 (M = Ti, 1; M = Zr, 2) and Tp*M(NMe2)3 (M = Ti, 3; M = Zr, 4) were prepared by the reactions of M(NMe2)3Cl (M = Ti, Zr) with sodium hydridotris(pyrazol-1-yl)borate and potassium hydridotris(3,5-dimethylpyrazol-1-yl)borate, respectively. The structures of 1, 2, and 4·CH2Cl2 were determined by X-ray diffraction and show octahedral coordination geometry around the metal centers. Density functional theory calculations at the B3PW91 level were performed to understand the orientations and the rotational behavior of amido ligands in these metal complexes.