Synthesis, electronic structures, and reactivity of mononuclear and dinuclear low-valent molybdenum complexes in iminopyridine and bis(imino)pyridine ligand environments.

Autor: Dissanayake AI; Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA., Hollingsworth TS; Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA., Kurup SS; Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA., Wannipurage D; Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA., Hamilton PN; BASF Corporation, 1609 Biddle Ave, Wyandotte, MI 48192, USA. Electronic address: patrick.hamilton@basf.com., Lord RL; Department of Chemistry, Grand Valley State University, Allendale, MI 49401, USA. Electronic address: lordri@gvsu.edu., Groysman S; Department of Chemistry, Wayne State University, 5101 Cass Ave, Detroit, MI 48202, USA. Electronic address: groysman@chem.wayne.edu.
Jazyk: angličtina
Zdroj: Journal of inorganic biochemistry [J Inorg Biochem] 2022 May; Vol. 230, pp. 111744. Date of Electronic Publication: 2022 Feb 02.
DOI: 10.1016/j.jinorgbio.2022.111744
Abstrakt: Molybdenum in redox non-innocent ligand environments features prominently in biological inorganic systems. While Holm and coworkers, along with many other researchers, have thoroughly investigated formally high-oxidation-state molybdenum (Mo(IV)-Mo(VI)) ligated by dithiolenes, less is known about molybdenum in other formal oxidation states and/or different redox-active ligand environments. This work focuses on the investigation of low-valent molybdenum in four different redox non-innocent nitrogen ligand type environments (mononucleating and dinucleating iminopyridine, mononucleating and dinucleating bis(imino)pyridine). The reaction of iminopyridine N-(2,6-diisopropylphenyl)-1-(pyridin-2-yl)methanimine (L 1 ) with Mo(CO) 3 (NCMe) 3 produced Mo(L 1 )(CO) 3 (NCMe). Mo(L 1 )(CO) 3 (NCMe) undergoes transformation to Mo(L 1 )(CO) 4 upon treatment with CS 2 or prolonged stirring in dichloromethane. The reaction of the open-chain dinucleating bis(iminopyridine) ligand N,N'-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis(1-(pyridin-2-yl)methanimine) (L 2 ) similarly produced an hexacarbonyl complex Mo 2 (L 2 )(CO) 6 (NCMe) 2 which also underwent transformation to the octacarbonyl Mo 2 (L 2 )(CO) 8 . Both complexes featured anti-parallel geometry of the chelating units. The oxidation of Mo(L 1 )(CO) 3 (NCMe) with I 2 resulted in Mo(L 1 )(CO) 3 I 2 . The reaction of mononucleating potentially tridentate bis(imino)pyridine ligand (L 3 ) (N-mesityl-1-(6-((E)-(mesitylimino)methyl)pyridin-2-yl)methanimine) with both Mo(CO) 3 (NCMe) 3 and Mo(CO) 4 (NCMe) 2 produced complexes Mo(L 3 )(CO) 3 (NCMe) and Mo(L 3 )(CO) 4 in which L 3 was coordinated in a bidentate fashion, with one imino sidearm unbound. The reaction of dinucleating macrocyclic di(bis(imino)pyridine) analogue (L 4 ) led to the similar chemistry of Mo 2 (L 4 )(CO) 6 (NCMe) 2 and Mo 2 (L 4 )(CO) 8 complexes. Treatment of Mo(L 3 )(CO) 3 (NCMe) with I 2 formed a mono(carbonyl) complex Mo(L 3 )(CO)I 2 in which molybdenum was formally oxidized and L 3 underwent coordination mode change to tridentate. The electronic structures of formally Mo(0) complexes in iminopyridine and bis(imino)pyridine ligand environments were investigated by density functional theory calculations.
(Copyright © 2022. Published by Elsevier Inc.)
Databáze: MEDLINE
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