Redox induced oxidative C–C coupling of non-innocent bis(heterocyclo)methanides

Abstract

Redox driven C-C bond formation has gained recent attention over the traditional sequence of oxidative addition, insertion and reductive elimination. In this regard, transient radical mediated diverse reactivity profile of...

Redox-Induced Intramolecular C–C Coupling of Acyclic Bis(2-pyridylmethylene)ethylenediamine on a Ru(acac)2 Platform

“…Multielectron redox reaction is known to perform a pivotal role in numerous biological and catalytic processes, which could be accomplished by the cooperativity between the redox-active metal and the suitably designed π-interacting ligands . Electron shuttling at the metal–ligand interface (M n L p ↔ M n +1 L p –1 ) due to the mixing of frontier molecular orbitals (MOs) may lead to valence tautomerism , or dynamic resonance phenomena , and that indeed promotes diverse reactivity . In this regard, Schiff-base-ligand-derived transition-metal complexes have drawn continuing attention primarily because of their tunable coordinating features, redox participation, and multifarious reactivity aspects .…”

Metal–ligand synergy driven functionalisation of alkylene linked bis(aldimine) on a diruthenium(ii) platform. Cyclisation versus oxygenation

“…7, Table 4, Table S48†). 22 The absence of the forbidden g 1/2 (Δ M s = 2) signal near 1600 G implied the non-interacting mode of spins onto the metal ions due to the presence of the non-conjugated aliphatic linker in L. 23 The two close by one-electron reductions of the ligand moiety resulted in doubly reduced biradical ligand bridged [(acac) 2 Ru II (μ-L˙˙ 2− )Ru II (acac) 2 ] 2− ( 2 2− –5 2− , S = 1) via the intermediate radical state of [(acac) 2 Ru II (μ-L˙ − )Ru II (acac) 2 ] − ( 2 − –5 − , S = 1/2, Scheme 2).…”

“…7, Table 4, Table S48 †). 22 The absence of the forbidden g 1/2 (ΔM s = 2) signal near 1600 G implied the non-interacting mode of spins onto the metal ions due to the presence of the non-conjugated aliphatic linker in L. 23 The two close by one-electron reductions of the ligand moiety resulted in doubly reduced biradical ligand bridged [(acac…”

Unique Metal–Ligand Interplay in Directing Discrete and Polymeric Derivatives of Isomeric Azole-Carboxylate. Varying Electronic Form, C–C Coupling, and Receptor Feature

“…The half-molecule in the asymmetric unit generated the dinuclear complex in [ 6 ]­(ClO 4 ) 2 through a crystallographic inversion center located at the midpoint of the C1–C2 bond (Figure ). The distorted octahedral situation around the metal ions yielded bite angles involving L2 2– of 78.06(12) and 80.0(2)° for 5 and [ 6 ]­(ClO 4 ) 2 , respectively. Though 5 /[ 6 ]­(ClO 4 ) 2 exhibited similar Ru-N1 (L2 2– ) distances of 2.074(3)/2.079(6) Å, an appreciable variation in Ru-O1 (L2 2– ) distances 2.107(2)/2.199(6) Å, respectively, developed due to the bridging effect in the latter case.…”

“…The present deliberation relating to the versatility of the azole-carboxylate-derived isomeric deprotonated H 2 L1 and H 2 L2 in directing diverse molecular frameworks in combination with selective ruthenium and osmium metal fragments as well as recognition of its redox noninnocence, in situ C–C coupling, and anion sensing events would prompt further exploration with other metal fragments from the broader perspectives of materials sciences and molecular functionalization …”