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Isolation of a Tetranuclear Intermediate Complex in the Synthesis of Paddlewheel‐Type Dirhodium Tetraacetate
Author(s) -
Kataoka Yusuke,
Yano Natsumi,
Kawamoto Tatsuya,
Handa Makoto
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.201500955
Subject(s) - chemistry , molecule , crystallography , crystal structure , solvent , infrared spectroscopy , ligand (biochemistry) , spectroscopy , absorption spectroscopy , stereochemistry , single crystal , nuclear magnetic resonance spectroscopy , x ray crystallography , diffraction , organic chemistry , optics , biochemistry , physics , receptor , quantum mechanics
Abstract To investigate the detailed mechanism of formation of the paddlewheel‐type dirhodium tetraacetate [Rh 2 (O 2 CCH 3 ) 4 (L) 2 ] ([ 1 ‐(L) 2 ]; L = axial‐coordinated solvent ligand), we performed a step‐by‐step synthesis. The isolated red intermediate complex [Rh 4 (μ‐Cl) 4 (O 2 CCH 3 ) 4 (L) 4 ] ([ 2 ‐(L) 4 ]) was characterized by means of single‐crystal X‐ray diffraction, 1 H NMR spectroscopy, infrared spectroscopy, and elemental analysis. The crystal structure of [ 2 ‐(MeOH) 4 ], which was crystallized from MeOH solution, has a unique twisted‐box Rh 4 (μ‐Cl) 4 core coordinated by four μ‐carboxylato bridging ligands and four MeOH molecules as axially coordinated solvent molecules. The electronic structure and absorption properties of [ 2 ‐(MeOH) 4 ] in MeOH were also carefully investigated both experimentally and theoretically.