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Variable Borohydride Hapticity in Nickel(II) Scorpionate Complexes [(TpR,Me)Ni(ηn‐BH4)]: TpR,Me = hydrotris{3‐R‐5‐methyl‐1‐pyrazolyl}borate; R = Ph, n = 3 vs. R = Me, n = 4
Author(s) -
Kruse Colin P.,
Deb Tapash,
Aboelenen Ahmed M.,
Anderson Caitlin M.,
Petersen Jeffrey L.,
Jensen Michael P.
Publication year - 2016
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.201501330
Subject(s) - chemistry , borohydride , nickel , steric effects , octahedron , pyrazole , ligand (biochemistry) , medicinal chemistry , boron , crystallography , inorganic chemistry , stereochemistry , catalysis , crystal structure , organic chemistry , biochemistry , receptor
A “second‐generation” scorpionate ligand was utilized to prepare the nickel(II) borohydride complex [(Tp Ph,Me )Ni(η 3 ‐BH 4 )], wherein the borohydride was coordinated through two bridging B–H bonds, leaving two terminal B–H bonds uncoordinated as determined by X‐ray crystallography. The distorted square‐pyramidal complex is paramagnetic ( S = 1), with 18 valence electrons, and contrasts with a previously reported 20‐electron pseudo‐octahedral “first‐generation” analogue, [(Tp Me,Me )Ni(η 4 ‐BH 4 )] (P. J. Desrochers, et al. Inorg. Chem . 2003 , 42 , 7945–7950). These distinct borohydride coordination modes were distinguished by FTIR spectroscopy, and rationalized by DFT calculations on simplified models, [(Tp)Ni(η n ‐BH 4 )] ( n = 3, 4). The difference in borohydride hapticities is attributed to the steric effect of the scorpionate 3‐pyrazole phenyl substituents disposed proximally to the metal, thus demonstrating the subtle versatility of Trofimenko's scorpionate ligands in controlling ligand field geometries. The precursor complex [(Tp Ph,Me )Ni(κ 2 ‐NO 3 )] was also prepared and characterized.