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Osmium(IV) Halide Complexes with Dimethyl Sulfoxide[H(dmso) 2 ][OsX 5 (dmso‐κ O )], X=Cl, Br: Synthesis, Structure, and Properties
Author(s) -
Rudnitskaya Olga V.,
Dobrokhotova Ekaterina V.,
Kultyshkina Ekaterina K.,
Tereshina Tatiana A.,
Trigub Alexander L.,
Zubavichus Yan V.,
Khrustalev Victor N.
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201904109
Subject(s) - osmium , orthorhombic crystal system , chemistry , crystallography , xanes , dimethyl sulfoxide , extended x ray absorption fine structure , acetone , crystal structure , halide , space group , x ray crystallography , stereochemistry , medicinal chemistry , inorganic chemistry , absorption spectroscopy , spectroscopy , diffraction , organic chemistry , ruthenium , physics , quantum mechanics , catalysis , optics
Two osmium complexes of common formula [H(dmso) 2 ][Os IV Х 5 (dmso‐κ O )] 1 (Х=Cl) and 2 (Х=Br) are synthesized via the reaction of H 2 OsX 6 (Х=Cl, Br) with DMSO. The complex 1 crystallized in the orthorhombic space group Pca2 1 . For 2 , two orthorhombic polymorphs are found, namely, 2 a in space group Cmcm and 2 b in space group Pbca . Within the [H(dmso) 2 ] + cations of 1 and 2 a , the cis ‐configuration of the DMSO moieties has been observed for the first time. The complexes are characterized by a set of spectroscopic (NMR, IR, UV‐Vis, EXAFS/XANES) and diffraction (single crystal and powder) techniques. Both complexes 1 and 2 retain their molecular structures in DMSO and acetone solutions, as evidenced by Os L 3 ‐edge EXAFS/XANES. 1 H NMR spectra of 1 and 2 in DMSO solutions reveal signals of coordinated DMSO. In acetone solutions, signals of the [H(dmso) 2 ] + cations are observed in addition to those of coordinated neutral DMSO.