Synthesis and characterization of bis(pyrazolyl)borate Ni(ii) complexes: ligand rearrangement and transformation.

Author(s) Zhao, Q.; Guan, X.T.; Dou, T.; Cao, H.J.; Ma, N.N.; Xu, T.; Gao, P.H.; Kong, X.H.; Zhang, J.; Chen, X.
Journal Dalton Trans
Date Published 2019 Aug 15
Abstract

Five examples of bis(pyrazolyl)borate Ni(ii) complexes 2-5, exhibiting C-HNi interactions, were readily prepared from the reactions of K[BBN(3-R1-4-R2-pz)2] with Ni(ii) precursors (Ni(acac)2 or NiCl2(PPh3)2) in dichloromethane or toluene. When R1 = R2 = H, complex 2a with square-planar geometry around the Ni centre and showing an unusual C-HNi anagostic interaction was obtained. In contrast, when R1 = Me, R2 = H or R1 = Me, R2 = Br, tetrahedral complexes 3 or 4 were formed preferentially with strong C-HNi agostic interactions, respectively. Additionally, some differences in the formation and transformation of 3 and 4 were also found including a 1,2-borotropic shift during the formation of 3 and a further geometrical transformation from tetrahedral 3 to square-planar 2b by the second 1,2-borotropic shift under continuous heating; in contrast, no ligand change and further conversion were found in 4. When the more hindered 3-iPr-substituted ligand 1d was introduced in the reaction, the hydrolysis and cleavage of one B-N bond in the ligand occurred, leading to the singly hydroxo-bridged complex 5. The experimental and theoretical results indicate that the preference to form a thermodynamically stable complex and then balancing with orbital energy should be the intrinsic reason for the reaction selectivity.

DOI 10.1039/c9dt02287b
ISSN 1477-9234
Citation Zhao Q, Guan X-, Dou T, Cao H-, Ma N-, Xu T, et al. Synthesis and characterization of bis(pyrazolyl)borate Ni(ii) complexes: ligand rearrangement and transformation. Dalton Trans. 2019.

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