Fine Tuning between Radical versus Nonradical States of Azoheteroarenes on Selective Osmium Platforms.

The article highlights the cooperative impact of azoheteroarenes [abbt: 2,2'-azobis(benzothiazole), L1-L3; bmpd: (E)-1,2-bis(1-methyl-1H-pyrazole-3-yl) diazene, L4] and coligands [bpy: 2,2'-bipyridine; pap: 2-phenylazopyridine] in tuning radical (N-N•-) versus nonradical (N═N0) states of L on selective OsII-platforms in structurally/spectroscopically characterized monomeric [1]ClO4-[6]ClO4 and [1](ClO4)2-[2](ClO4)2/[7](ClO4)2-[8](ClO4)2, respectively. The preferred syn-configuration of L in the complexes prevented obtaining ligand bridged dimeric species. It revealed that {Os(bpy)2} facilitated the stabilization of both nonradical ([1](ClO4)2-[2](ClO4)2) and radical ([1]ClO4-[2]ClO4) states of L1/L2, while it delivered exclusively the radical form for L3 in [3]ClO4. In contrast, {Os(pap)2} generated radical states of L1-L3 in [4]ClO4-[6]ClO4, respectively, without any alteration of the redox state of OsII and azo (N═N0) function of the pap coligand. The neutral state of L4 was, however, ascertained in [7](ClO4)2 or [8](ClO4)2 irrespective of the nature of the metal fragment {Os(bpy)2} or {Os(pap)2}, respectively. Switching between radical and nonradical forms of L in the complexes as a function L and coligand could be addressed based on their relative FMO (frontier molecular orbital) energies. Multiple close redox steps of the complexes extended a competitive electron transfer scenario between the redox active components including metal/L/bpy/pap, leading to delicate electronic forms in each case.

Sequential Oxygenation of Bis(ß-diketiminate) on a Selective Diruthenium Platform.

This article demonstrated the redox-noninnocent phenylene-linked bis(ß-diketiminate) (L2-)-bridged first example of isomeric diruthenium(III)-acac species (acac = acetylacetonate) and its ability to activate dioxygen. The coordination of deprotonated L2- to the {Ru(acac)2} in bis(bidentate) mode led to isomeric {(acac)2RuIII}2(µ-L2-) (S = 1, 1-trans/1-cis, green). 1 displayed Ru(III)-based anisotropic EPR in CH3CN but without the resolution of the forbidden (ΔMs = 2) g1/2 signal at 77 K. 1-cis, however, slowly transformed to the energetically favored 1-trans form. 1 underwent two-step oxygenation at the Cß sites of L2- to form the ß-diketiminate/α-ketodiimine (L'-)-bridged mixed valent (acac)2RuIII(µ-L'-)RuII(acac)2 (2, S = 1/2, pink) followed by bis(α-ketodiimine) (L″)-bridged isovalent (acac)2RuII(µ-L″)RuII(acac)2 (3, S = 0, red). The role of O2 toward 1 → 2/3 was corroborated by 18O2 labeling experiment. Redox steps of 1-3 varied as a function of isomeric identity, bridge, and metal oxidation state. The calculated MOs and Mulliken spin densities attributed to the noninnocence of L2-, L'-, and L″ in the respective complexes. Spectrophotometric monitoring of 1 → 2 revealed pseudo-first-order rate constants (105k s-1) of 1.8 (303 K), 3.5 (313 K), 7.7 (323 K), and 17.0 (333 K) and ΔH⧧/ΔS⧧/ΔG⧧ of 14.3 kcal mol-1/-33.1 cal mol-1 K-1/24.2 kcal mol-1 (298 K), respectively. Moreover, characterization of the short-lived blue intermediate obtained during the conversion of 1 → 2/3 upon exposure to O2 supported its valence tautomeric form (VT1, RuIII-L2--RuIII ↔ RuIII-L•--RuII, S = 1), which in effect facilitated oxygen activation at the ligand backbone.

On the Question of S-S Bond Cleavage of 2,2'-Dithiodipyridine on Selective Ru and Os Platforms. MLCT or Hydride or Solvent Mediated Event.

This article deals with the S-S bond scission of the model substrate 2,2'-dithiodipyridine (DTDP) in the presence of a selective set of metal precursors: RuII(acac)2, [RuIICl2(PPh3)3], [RuIIHCl(CO)(PPh3)3], [RuII(H)2(CO)(PPh3)3], [RuII(bpy)2Cl2], [RuII(pap)2Cl2], [OsII(bpy)2Cl2], and [OsII(pap)2Cl2] (acac, acetylacetonate; bpy, 2,2'-bipyridine; pap, 2-phenylazopyridine). This led to the eventual formation of the corresponding mononuclear complexes containing the cleaved pyridine-2-thiolate unit in 1-4/[5]ClO4-[8]ClO4. The formation of the complexes was ascertained by their single-crystal X-ray structures, which also established sterically constrained four-membered chelate (average N1-M-S1 angle of 67.89°) originated from the in situ-generated pyridine-2-thiolate unit. Ruthenium(III)-derived one-electron paramagnetic complexes 1-2 (S = 1/2, magnetic moment/B.M. = 1.82 (1)/1.81(2)) exhibited metal-based anisotropic electron paramagnetic resonance (EPR) (Δg: 1/2 = 0.64/0.93, ⟨g⟩: 1/2 = 2.173/2.189) and a broad 1H nuclear magnetic resonance (NMR) signature due to the contact shift effect. The spectroelectrochemical and electronic structural aspects of the complexes were analyzed experimentally in combination with theoretical calculations of density functional theory (DFT and TD-DFT). The unperturbed feature of DTDP even in refluxing ethanol over a period of 10 h can be attributed to the active participation of the metal fragments in facilitating S-S bond cleavage in 1-4/[5]ClO4-[8]ClO4. It also revealed the following three probable pathways toward S-S bond cleavage of DTDP as a function of metal precursors: (i) the metal-to-ligand charge-transfer (MLCT) (RuII → σ* of DTDP)-driven metal oxidation (RuII → RuIII) process in the case of relatively electron-rich metal fragments {RuII(acac)2} or RuIICl2 in 1 or 2, respectively; (ii) metal hydride-assisted formation of 3 or 4 with the concomitant generation of H2; and (iii) S-S bond reduction with the simultaneous oxidation of the solvent benzyl alcohol to benzaldehyde.

Inner-Sphere Electron Transfer Induced Reversible Electron Reservoir Feature of Azoheteroarene Bridged Diruthenium Frameworks.

This article demonstrates the stabilization of ground- and redox-induced metal-to-ligand charge transfer excited states on coordination of azo-coupled bmpd(L4) [bmpd = (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene; L4 = -N═N-] to the electron-rich {Ru(acac)2} (acac = acetylacetonate) unit in mononuclear RuII(acac)2(L4) (1) and diastereomeric dinuclear (acac)2Ru2.5(µ-L4•-)Ru2.5(acac)2 [rac, ΔΔ/ΛΛ (2a)/meso, ΔΛ (2b)] complexes, respectively. It also develops further one-step intramolecular electron transfer induced L4•- bridged isovalent higher analogue [(acac)2RuIII(µ-L4•-)RuIII(acac)2]ClO4 in diastereomeric forms, rac-[2a]ClO4/meso-[2b]ClO4. On the contrary, under identical reaction conditions electronically and sterically permuted bimpd [L5, (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene)] delivered mononuclear RuII(acac)2(L5) (3) as an exclusive product. Further, the generation of unprecedented heterotrinuclear complex [(acac)2RuII(µ-L4)AgI(µ-L4)RuII(acac)2]ClO4 ([4]ClO4) involving unreduced L4 via the reaction of 1 and AgClO4 revealed the absence of any inner-sphere electron transfer (IET) as in precursor 1, which in turn reaffirmed an IET (at the interface of electron-rich Ru(acac)2 and acceptor L4) mediated stabilization of 2. Structural authentication of the complexes with special reference to the tunable azo distance (N═N, N-N•-, N-N2-) of L and their spectro-electrochemical events in accessible redox states including the reversible electron reservoir feature of 2 → 2+/2+ → 2 were evaluated in conjunction with density functional theory/time-dependent density functional theory calculations. The varying extent of IET as a function of heteroaromatics appended to the azo group of L (L1 = abpy = 2,2'-azobipyridine, L2 = abbt = 2,2'-azobis(benzothiazole), L3 = abim = azobis(1-methylbenzimidazole), L4 and L5, Schemes 1 & 2) in the Ru(acac)2-derived respective molecular setup has been addressed.

Host-Guest Feature of DPPP Bridged Arene-Ruthenium Clip Derived Molecular Rectangle.

The development of DPPP2- (H2DPPP = 2,5-dihydro-3,6-di-2-pyridylpyrrolo(3,4-c)pyrrole-1,4-dione) bridged (NN∩NN) diruthenium complexes [(Cym)(X)RuII(µ-dppp)RuII(X)(Cym)] (Cym = para-cymene and X = OTf- (1), SCN- (2), N3- (3), NO2-(4)) are considered as the probable molecular clips for the construction of metallarectangle. Crystal structures of 2-4 established anticonfiguration with respect to monodentate SCN-, N3- and NO2- groups, respectively. Though molecular clips 2-4 failed to provide the desired metallarectangle in combination with the 4,4'-bipyridine spacer, 1 with the labile OTf groups facilitated to achieve the metallarectangle 5. The crystal structure of 5 revealed that two twisted 4,4'-bipyridine spacers bridged between the two units of dimeric 1 in symmetric fashion, which in effect led to the newer class of molecular rectangle 5 with a hydrophobic cavity size of the cationic host of 8.32 × 11.11 Å2. Furthermore, the host-guest interaction potential of 5 with special reference to the guest molecule, pyrene, was explored. The crystal structure of the resultant molecule 6 ascertained the partial encapsulation of two pyrene molecules inside the hydrophobic cavity of 5, due to the twisted 4,4'-bipyridine spacer units between the two ruthenium clips. It also attributed a noncovalent CH-π interaction involving protons of pyrene and the π-electron cloud of 4,4'-bipyridine as well as a weak interaction between pyrene protons and the pendant C═O group of DPPP. Encapsulation of the guest molecule (pyrene) inside the cavity of the metallarectangle was also monitored by following the quenching of florescent intensity of pyrene on addition of 5.

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

This article addresses the impact of metal-ligand redox cooperativity on the functionalisation of coordinated ligands. It demonstrates the structure-reactivity correlation of bis(aldimine) derived bis-bidentate L (Py-CHN-(CH2)n-NCH-Py, with n = 2 (L1), 3 (L2), 4 (L3)) as a function of the conformation (syn/anti) of its alkylene linker as well as the overall structural form (cis/trans) of (acac)2RuII(µ-L)RuII(acac)2 complex moieties (1-5) possessing an electron-rich acetylacetonate (acac) co-ligand. A systematic variation of the bridging alkylene unit of L in RuII/RuII-derived 1-5 led to the following reactivity/redox events, which were validated through structural, spectroscopic, electrochemical and theoretical evaluations: (i) Cyclisation of the ethylene linked (syn conformation) bis-aldimine unit of L1 via C-C coupling yielded pyrazine bridged (acac)2RuII(µ-L1')RuII(acac)2, 1a, while the corresponding anti-form (ethylene linker) of the metal-bound L1 in 2 ((acac)2RuII(µ-L1)RuII(acac)2) led to oxygenation at the ligand backbone (bis-aldimine (L) → bis(carboxamido) (L'')) via O2 activation to generate RuIIIRuIII-derived (acac)2RuIII(µ-L1''2-)RuIII(acac)2 (2a). (ii) Consequently, propylene and butylene linked L2 and L3 bridged between two {Ru(acac)2} units in 3 and 4/5 underwent oxygenation of L to L'' to yield diruthenium(III) complexes 3a and 4a/5a, respectively. (iii) In contrast, analogous L bridged oxidised [(acac)2RuIII(µ-L)RuIII(acac)2](ClO4)2 ([2](ClO4)2-[5](ClO4)2) and [{(PPh3)2(CO)(H)RuII}2(µ-L)](ClO4)2 ([6](ClO4)2-[8](ClO4)2) involving electron poor co-ligands failed to undergo the oxygenation of L irrespective of its n value, reemphasising the effective role of redox interplay between RuII and L particularly in the presence of an electron-rich acac co-ligand in the functionalisation of the latter in 1a-5a.

The isomer-sensitive electrochemical HER of ruthenium(II)-hydrido complexes involving redox-active azoheteroaromatics.

The article deals with the development of isomeric ruthenium(II)-hydrido complexes [RuII(H)(L1)(PPh3)2(CO)]ClO4 ([1a]ClO4-[1b]ClO4)/[RuII(H)(L2)(PPh3)2(CO)]ClO4 ([2a]ClO4-[2b]ClO4) involving azo coupled L1 [L1: (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene]/L2 [L2: (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene], respectively. Structural evaluation of the complexes affirmed the syn conformation of the coordinated/uncoordinated pyrazole groups of L and its unperturbed neutral azo (NN) state. Isomeric forms in [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 differed with respect to the cis and trans orientations of the coordinated CO and N(azo) donor of L, respectively. It also demonstrated the formation of intermolecular hydrogen-bonded dimeric or 1D-polymeric chains in [1a]ClO4/[2b]ClO4 or [1b]ClO4, respectively. Successive two-electron reductions of the complexes varied to an appreciable extent as a function of the heterocycles connected to L. The involvement of the azo function of L towards the reductions ([NN]0 → [NN]˙- → [NN]2-) was supported by the DFT calculated MOs and Mulliken spin density at the paramagnetic state, which was further validated by the radical EPR profile of the first reduced (S = 1/2) state. Isomeric [1a]ClO4/[1b]ClO4 or [2a]ClO4/[2b]ClO4 immobilised on the carbon cloth support underwent various electrochemical acidic HERs (hydrogen evolution reactions) with TOF/10-1 s-1: [1a]ClO4 (0.83) > [1b]ClO4 (0.68) > [2a]ClO4 (0.50) > [2b]ClO4 (0.37).

Donor-acceptor bridge 2,5-bis(2-oxido-phenyl)thiazolo-[5,4-d]thiazole derived diruthenium and diosmium systems. Structural and competitive electronic events as a function of metal ion, bridge and ancillary ligand.

The article deals with the structural and electronic forms of hitherto unexplored L2- (H2L = 2,5-bis(2-hydroxyphenyl)thiazolo-[5,4-d]thiazole) bridged analogous diruthenium [{(AL1/AL2)2 RuII}2(µ-L2-)]2+ [1](ClO4)2/[2](ClO4)2 and diosmium [{(AL1/AL2)2OsII}2(µ-L2-)]2+ [3](PF6)2/[4](ClO4)2 complexes as a function of moderate-to-strongly π-accepting ancillary ligands: AL1 = 2,2'-bipyridine (bpy) and AL2 = 2-phenylazopyridine (pap). Structural elucidation of the complexes established an anti-oriented bridge (L2-) linked to the metal units through its N,O-/O-,N-donor sets, which led to two six-membered chelates in each case. It also highlighted the twisting of the phenolato functions of L2- with respect to the central thiazolothiazole (TzTz) unit and the unreduced state of the azo function of AL2 and multiple non-covalent π⋯π/CH⋯π interactions within the molecules in the nearby asymmetric units. The potential of the multiple redox steps of the complexes varied as a function of Ru versus Os and AL1 versus AL2. A collective consideration of experimental and DFT calculations revealed largely bridge- and metal-based first and second oxidative steps, which could be attributed to the electronic forms [(AL1/AL2)2MII(µ-L˙-)MII(AL1/AL2)2]3+ ↔ [(AL1/AL2)2MII(µ-L2-) MIII(AL1/AL2)2]3+ and [(AL1/AL2)2M2.5(µ-L˙-) M2.5(AL1/AL2)2]4+ for 13+-43+ and 14+-44+, respectively, implying the noninnocence of L2-, which was enhanced on moving from bpy to pap and from Os to Ru. Reductions of 12+-42+ were, however, centred around the ancillary ligand (AL1/AL2), in spite of the π-accepting feature of the TzTz core of L, implying the weaker π-acceptor form of the latter with special reference to the former. Involvement of the primarily metal (with minor contribution of the bridge, L) and ancillary ligand (AL) based orbitals in the second oxidised and first reduced steps could also be corroborated by the metal-based anisotropic and free radical EPR spectral signatures, respectively. 12+-42+ displayed multiple moderately-intense-to-intense charge-transfer absorption bands in the visible-to-UV region, which originated from mixed metal/ligand and intra/inter-ligand charge-transfer transitions.

Diosmium compounds containing bis(imidazole)-p-quinone bridging ligands.

The doubly deprotonated bridging ligand L12- derived from 2,6-bis(2-pyridyl)-1,5-dihydro-1',4'-benzoquinono[2',3'-d:5',6'-d']diimidazole H2L1 forms coordination compounds with two bis(2,2'-bipyridine)osmium(II) complex fragments in anti ([1](ClO4)2) and syn configurations ([2](ClO4)2) of {(µ-L1)[Os(bpy)2]2}(ClO4)2, as evident from crystal structure analyses. Exchange of the metal-coordinating 2-pyridyl functions in the bridge through non-coordinating 4-tolyl substituents (L12- → L22-) leads to [3](ClO4)2 which involves chelation of the [Os(bpy)2]2+ groups through imidazole-N and carbonyl-O atoms of the central p-quinone function. In addition to identification, the compounds were subjected to electrochemical (CV, DPV) and spectroelectrochemical (UV-vis-NIR, EPR) analyses of electron transfer, the results being supported by results from TD-DFT calculations. Essential differences between [1n+]/[2n+] and [3n+] systems were found regarding variable but mostly metal centred oxidation, the two processes separated much more for [3n+]. The first reduction is bpy ([1+], [2+]) or quinone ligand centred ([3+]). Electronic structures and electron transfer behaviour are thus highly sensitive to differences of configuration and coordination.

Redox induced S-S bond cleavage of 2,2'-dithiobisbenzothiazole - leading to a [2Ru-2S] core analogous to [2Fe-2S] cluster.

Facile reduction of 2,2'-dithiobisbenzothiazole by the mediation of metal-to-ligand charge transfer or by internal reducing equivalent is demonstrated. It leads to various binding modes of thiolates (κ1, κ2, µ) in a series of mononuclear and dinuclear ruthenium complexes. The dinuclear complex exhibited electron transfer processes similar to a [2Fe-2S] cluster.

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

Redox driven C-C bond formation has gained recent attention over the traditional sequence of oxidative addition, insertion and reductive elimination reactions. In this regard, the transient radical mediated diverse reactivity profile of bis(heterocyclo)methanes (H-BHM: HL1-HL4) has been demonstrated as a function of varying metal ions and ligand backbones. It highlighted the following events: (a) redox induced homocoupling of deprotonated HL1 and HL4 on coordination to M(OAc)2 precursors (M = CuII, ZnII, PdII, AgI), including the effective role of molecular oxygen in the transformation process; (b) steric inhibition of C-C coupling of HL1 or HL4 on inserting the substituent at the bridged methylene centre (Ph in HL2 or CH3 in HL3); (c) competitive C-C coupling versus oxygenation of free HL1 with varying concentrations of PdII(OAc)2 as the ease of oxygenation over dimerisation of the deprotonated HL1 was corroborated by the DFT calculated lower activation barrier and greater thermodynamic stability of the former; and (d) redox non-innocence of BHMs on a coordinatively inert ruthenium platform, which in turn favored the involvement of a radical pathway for the aforestated coupling or oxygenation process. A combined structural, spectroscopic and DFT calculated transition state analysis demonstrated the mechanistic outline for the metal assisted oxidative coupling of BHMs.