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Non‐Spectator Feature of α‐Diimine Mimicked Di/tetrahydro‐bisisoquinoline and Biimidazopyridine on {Ru(acac) 2 } Platform
Author(s) -
Panda Sanjib,
Goel Puneet,
Lahiri Goutam Kumar
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.202000230
Subject(s) - chemistry , diimine , dehydrogenation , imine , ligand (biochemistry) , nucleophile , ruthenium , intramolecular force , medicinal chemistry , yield (engineering) , stereochemistry , photochemistry , catalysis , organic chemistry , biochemistry , materials science , receptor , metallurgy
The diverse reactivity profiles of α‐diimine analogues, di/tetrahydro‐bisisoquiniline (L1–2H/L2–4H), and biimidazopyridine (L3) have been illustrated on the {Ru(acac) 2 } platform (acac=acetylacetonate). Increasing Lewis acidity on coordination to {Ru(acac) 2 } as well as fine tuning of ligand backbone led to oxidative dehydrogenation of L1–2H/L2–4H to yield metallated bisisoquinoline (BIQ) and unexplored C–C coupling/nucleophilic attack assisted ring opening reactions at L3 to rearrange into modified metallated amidate functions. Preformed L1–4H involving amine functionality underwent in situ transformation to imine in [Ru II/III (acac) 2 (L1–2H)] n + ( 1 n + , n = 0,1), followed by dehydrogenation to yield [Ru II/III (acac) 2 (BIQ)] n + ( 2 n + , n = 0,1). Analogous complex [Ru II (acac) 2 (L2–4H)] n + ( 3 n + , n = 0,1) encompassing diimine (L2–4H) ligand also participated in similar dehydrogenation process to generate 2 n + . On the other hand, reaction of L3 with {Ru(acac) 2 } led to the simultaneous formation of three products: [Ru III (acac) 2 (L3)]ClO 4 ([ 4 ]ClO 4 ) incorporating unperturbed N,N ‐donating L3 and [Ru III (acac)(L4)] ( 5 )/[Ru III (acac) 2 (L5)] ( 6 ) with functionalized L3. Involvement of intramolecular C–C coupling between the methine carbon of acac and L3 or the intermolecular nucleophilic attack of H 2 O at L3, resulted in functionalized L4 or L5 in 5 or 6 , respectively. Authentication of the isolated products was made via structural, electrochemical and spectral details along with theoretical support.