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Synthesis and Molecular Structure of Pseudo‐Hexacoordinated Pnictines Bearing 2‐Phenylpyridine Ligands
Author(s) -
Sakabe Masato,
Ooizumi Akihisa,
Fujita Wataru,
Aoyagi Shinobu,
Sato Soichi
Publication year - 2020
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.202000795
Subject(s) - pnictogen , chemistry , crystallography , natural bond orbital , lone pair , crystal structure , stibine , molecule , stereochemistry , phosphine , organic chemistry , catalysis , physics , superconductivity , arsine , quantum mechanics
The pseudo‐hexacoordinated organo‐pnictogen(III) compounds tris[2‐(2‐pyridyl)phenyl]stibine [(ppy) 3 Sb, 1 ] and tris[2‐(2‐pyridyl)phenyl]bismuthine [(ppy) 3 Bi, 2 ], which bear three 2‐phenylpyridine (ppy) ligands, were prepared and isolated from the reaction of 2‐(2‐lithiophenyl)pyridine with the corresponding pnictogen(III) chloride (PnCl 3 ; Pn = Sb, Bi). Compounds 1 and 2 were characterized using NMR spectroscopy, mass spectrometry, and elemental analysis. Their solid‐state structures were determined using single‐crystal X‐ray diffraction analysis, which revealed similar pseudo‐hexacoordinated, distorted facial octahedral bonding geometries around the central pnictogen atoms, wherein the three pyridyl groups coordinate to the pnictogen atoms via three weak LP(N)→σ*(Pn–C) donor–acceptor interactions. Natural bond orbital (NBO) and atoms in molecules (AIM) analyses were used to characterize the weak ionic interactions between the nitrogen and pnictogen atoms. The HOMOs of 1 and 2 correspond to the lone pairs of electrons on the central pnictogen atom, which indicates that these compounds can be classified as 14–Pn–6 chemical species.