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Scorpionato Halide Complexes [(Tp Ph,Me )Ni–X] [X = Cl, Br, I; Tp Ph,Me = Hydrotris(3‐phenyl‐5‐methyl‐1‐pyrazolyl)borate]: Structures, Spectroscopy, and Pyrazole Adducts
Author(s) -
Deb Tapash,
Anderson Caitlin M.,
Ma Huaibo,
Petersen Jeffrey L.,
Young Victor G.,
Jensen Michael P.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402897
Subject(s) - chemistry , adduct , pyrazole , halide , iodide , crystallography , bond length , intramolecular force , hydrogen bond , inorganic chemistry , medicinal chemistry , ligand (biochemistry) , crystal structure , stereochemistry , molecule , organic chemistry , biochemistry , receptor
Pseudotetrahedral scorpionato halide complexes [(Tp Ph,Me )Ni–X] [Tp Ph,Me = hydrotris(3‐phenyl‐5‐methyl‐1‐pyrazolyl)borate] were synthesized by metathesis of Tl(Tp Ph,Me ) and NiX 2 (X = Cl, Br, I). Pyrazole adducts [(Tp Ph,Me )Ni(Hpz Ph,Me )(X)] (X = Cl, I) were also obtained. [(Tp Ph,Me )Ni–X] (X = Br, I) are isomorphous with previously reported [(Tp Ph,Me )Ni–Cl], and a new solvated pseudo‐polymorph [(Tp Ph,Me )Ni–Cl] · 2CH 2 Cl 2 was found in this work. Ni–X bond lengths correspond to ionic radii of the halide ions, but some variations in Ni–Cl and Ni–N bond lengths are respectively attributed to bending of the chloride from the ideal threefold HB ··· Ni axis and to the size of the 3‐pyrazole substituents. Electronic spectra were rationalized by means of time‐dependent (TD) DFT calculations on simplified C 3 v ‐symmetric [(Tp)Ni–X] models. Exogenous pyrazole binds to give the pentacoordinate adducts [(Tp Ph,Me )Ni(Hpz Ph,Me )(X)] (X = Cl, I). We obtained a crystal structure of the iodide adduct, as well as that of [(Tp Ph,Me )Ni(Hpz Ph,Me )(Cl)] · 0.5MeCN, isomorphous with a previously reported aquo monosolvate. A hallmark of adduct formation is an intramolecular N–H ··· X hydrogen bond between the added pyrazole and the adjacent halide ligand, thus giving rise to a strong IR absorption band. The stretching frequency correlates to the N(H) ··· X separation for the range of known adducts.