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Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform
Author(s) -
Singh Aditi,
Dey Sanchaita,
Panda Sanjib,
Lahiri Goutam Kumar
Publication year - 2021
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.202000918
Subject(s) - chemistry , intramolecular force , moiety , reactivity (psychology) , ligand (biochemistry) , dehydrogenation , bond cleavage , substituent , redox , photochemistry , medicinal chemistry , electrochemistry , intermolecular force , stereochemistry , molecule , inorganic chemistry , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , electrode , pathology
Redox induced ligand centered reactivity has garnered significant attention in recent times. In this context, the present article described intermolecular oxygenation, dehydrogenation and C−N bond cleavage processes of structurally robust picolylamine derivatives (HL) on selective {Ru(acac) 2 } metal platform encompassing electron rich acac (=acetylacetonate) co‐ligand. The diverse functionalization of {Ru(acac) 2 } coordinated β‐ketoiminate embedded picolylamines under basic condition included (i) oxygenation of methylene (C α ) position of picolyl fragment (−CH 2 −NH−→−CO−NH−), (ii) dehydrogenation of phenyl substituted C α (−CH−NH−→−C=N−) and (iii) C−N bond cleavage of the picolinoyl moiety to yield picolinate (−CO−N − −→−CO−O − ). Besides structural, spectroscopic (mass, 1 H/ 13 C−NMR, EPR, UV‐vis.) and electrochemical authentication of the products, correlation of the reactivity pattern was addressed via transition state (TS) calculations. Theoretical results supported the consideration of a common dianionic intermediate to address the aforementioned reactivities. The pertinent question of intramolecular cyclization versus intermolecular oxygenation of picolylamine on simple switching from {Ru(Cl)(H)(CO)(PPh 3 ) 3 } (earlier work [4a] ) metal fragment to {Ru(acac) 2 } (present report) was also elaborated by TS calculation.