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).

Nitrogen substitution induced lattice contraction in nickel nanoparticles for electrochemical hydrogen evolution from simulated seawater.

Herein, we demonstrate a facile method for the introduction of nitrogen in the lattices of nickel nanoparticles to form NiNx (x = 0.13, 0.20, 0.27). X-ray absorption spectroscopy reveals the contraction of the Ni-Ni bond and modulated coordination environment after nitrogen introduction. The NiN0.20 required 87 mV overpotential for -10 mA cm-2 cathodic current density in simulated seawater. The density functional theory calculations revealed favorable EH2Oads and ΔGHads after N-introduction.

Ruthenium Azobis(benzothiazole): Electronic Structure and Impact of Substituents on the Electrocatalytic Single-Site Water Oxidation Process.

The present article deals with the structurally and spectroelectrochemically characterized newer class of ruthenium-azoheteroarenes [RuII(Ph-trpy)(Cl)(L)]ClO4, [1]ClO4-[3]ClO4 (Ph-trpy: 4'-phenyl-2,2':6',2″-terpyridine; L1: 2,2'-azobis(benzothiazole) ([1]ClO4); L2: 2,2'-azobis(6-methylbenzothiazole) ([2]ClO4); L3: 2,2'-azobis(6-chlorobenzothiazole) ([3]ClO4)). A collective consideration of experimental (i.e., structural and spectroelectrochemical) and theoretical (DFT calculations) results of [1]ClO4-[3]ClO4 established selective stabilization of (i) the unperturbed azo (N═N)0 function of L, (ii) the exclusive presence of the isomeric form involving the N(azo) donor of L trans to Cl, and (iii) the presence of extended, hydrogen-bonded trimeric units in the asymmetric unit of [2]ClO4 (CH---O) via the involvement of ClO4- anions. The detailed electrochemical studies revealed metal-based oxidation of [RuII(Ph-trpy)(Cl)(L)]+ (1+-3+) to [RuIII(Ph-trpy)(Cl)(L)]2+ (12+-32+); however, the electronic form of the first reduced state (1-3) could be better represented by its mixed RuII(Ph-trpy)(Cl)(L•-)/RuIII(Ph-trpy)(Cl)(L2-) state. Both native (1+-3+) and reduced (1-3) states exhibited weak lower energy transitions within the range of 1000-1200 nm. Further, [1]ClO4-[3]ClO4 delivered an electrochemical OER (oxygen evolution reaction) process in alkaline medium on immobilizing them to a carbon cloth support, which divulged an amplified water oxidation feature for [2]ClO4 due to the presence of electron-donating methyl groups in the L2 backbone. The faster OER kinetics and high catalytic stability of [2]ClO4 could also be rationalized by its lowest Tafel slope (85 mV dec-1) and choronoamperometric experiment (stable up to 12 h), respectively, along with high Faradic efficiency (∼97%). A comparison of [2]ClO4 with the reported analogous ruthenium complexes furnished its excellent intrinsic water oxidation activity.

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.

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.

Dioxygen Activation by Redox-Active Bis(aldimine) Ligand Bridged Diruthenium Complex Possessing Singlet Ground State.

The unexplored 'actor' behavior of redox-active bis(aldimine) congener, p-phenylene-bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2 } (acac= acetylacetonate). Reaction under aerobic condition led to the one-pot generation of dinuclear complexes with unperturbed L1, imino-carboxamido (L2- ), and bis(carboxamido) (L32- )-bridged isovalent {RuII (µ-L1)RuII }, 1/ {RuIII (µ-L32- )RuIII }, 3 and mixed-valent {RuII (µ-L2- )RuIII }, 2. Authentication of the complexes along with the redox non-innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3 O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2/3.

Diruthenium and triruthenium compounds of the potential redox active non-chelated η1-N,η1-N-benzothiadiazole bridge.

In the present study, a series of non-chelated BTD (2,1,3-benzothiadiazole)-bridged diruthenium(II) ([{(CH3CN)(acac)2RuII}2(µ-BTD)] 1, [{CH3CN(acac)2RuII}(µ-BTD){RuII(acac)2(η1-N-BTD)}] 2, [{(η1-N-BTD)(acac)2RuII}2(µ-BTD)] 3), and triruthenium ([{(acac)2RuII}3(µ-BTD)2(η1-N-BTD)2] 4) complexes with varying ratios of η1-N and µ-bis-η1-N,η1-N modes of BTD were studied. Complexes 1-4 (S = 0) were obtained via the one-pot reaction of electron-rich Ru(acac)2(CH3CN)2 and electron-deficient BTD in refluxing acetone. The relatively low Ru(II)/Ru(III) potential of 1-4 (0.08-0.44 V versus SCE) further facilitated the isolation of the corresponding mixed valent RuIIRuIII (S = 1/2) and RuIIRuIIRuIII (S = 1/2)/RuIIRuIIIRuIII (S = 1) forms [1]ClO4-[3]ClO4 and [4]ClO4/[4](ClO4)2, respectively. The single-crystal X-ray structures of the representative mixed valent [1]ClO4 and [3]ClO4 established (i) Ru⋯Ru distances of 6.227 Å and 6.256 Å (molecule A)/6.184 Å (molecule B), respectively, (ii) a significant variation of the N-S distance of BTD in [3]ClO4 as a function of its binding mode µ versus η1 and (iii) similar Ru-N (µ-BTD) distances in each case corresponding to a valence delocalised situation. The mixed valent diruthenium (1+-3+) and triruthenium (4+/42+) complexes exhibited metal-based anisotropic electron paramagnetic resonance (EPR) and moderately intense low-energy intervalence charge-transfer (IVCT) transitions in the near-infrared region of 1730-1890 nm. Analysis of the IVCT band using the Hush treatment revealed a valence delocalised class III mixed valent state with the electronic coupling Vab of ≈2640-2890 cm-1, as also corroborated by the Kc values of 105-108, solvent independency of the IVCT band and uniform spin distribution between the metal ions in the singly occupied state(s). Furthermore, the involvement of the BTD (η1 and µ)-based orbitals in the reduction processes was evident by its free radical EPR feature.

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

The paper documents redox-triggered C-C coupling of acyclic N,N'-bis(2-pyridylmethylene)ethylenediamine (BPE) to yield 2,3-bis(2-pyridyl)pyrazine (DPP) upon coordination to an electron-rich {Ru(acac)2} (acac = acetylacetonate) unit. This led to DPP-bridged [{Ru(acac)2}2(DPP)]0/+ (2 and [2]ClO4) along with the unperturbed BPE-bridged [{Ru(acac)2}2(BPE)] (1). On the contrary, electron-poor {Ru(Cl)(H)(CO)(PPh3)3} yielded BPE-bridged [3](ClO4)2 as an exclusive product. Synergistic metal (Ru)-ligand (BPE) redox participation toward chemical noninnocence of the Schiff base ligand and DPP-mediated electronic communication in RuIIRuIII-derived [2]ClO4 are addressed.

Inner-sphere electron transfer at the ruthenium-azo interface.

Metal complexes exhibiting multiple reversible redox states have drawn continuing research interest due to their electron reservoir features. In this context, the present article describes ruthenium-acac complexes (acac = acetylacetonate) incorporating redox-active azo-derived abim (azobis(1-methylbenzimidazole)) in mononuclear [RuII(acac)2(abim)] (1) and dinuclear [{RuIII(acac)2}2(µ-abim2-)] (2)/[{RuIII(acac)2}2(µ-abim˙-)]ClO4 ([2]ClO4) frameworks. Structural, spectroscopic, electrochemical, and theoretical analysis of the complexes revealed the varying redox states of the azo functionality of abim, i.e., [-NN-]0, [-NN-]˙-, and [-N-N-]2- in 1, [2]ClO4, and 2, respectively. Comparison between the calculated azo bond distances of analogous {Ru(acac)2}-coordinated azoheteroaromatics, i.e., abim and previously reported abbt (azobis(benzothiazole)) and abpy (azobis(pyridine)) examples, revealed the impact of varying amounts of intramolecular metal-to-azo electron transfer (i.e., the case of back-bonding) on stabilising radical anionic ([-NN-]˙-) and hydrazido ([-N-N-]2-) bridging modes in the complexes. An evaluation of the electronic forms of the complexes in accessible redox states via combined experimental and theoretical studies suggested a preferred resonance configuration rather than a precise description, primarily due to the severe mixing of metal-abim frontier orbitals. Moreover, the newly developed corresponding Cu-abim complex [CuI2(µ-abim)3](BF4)2 ([3](BF4)2) demonstrated the unique scenario of varying bridging modes of abim within the same molecular unit, involving both coordinated and non-coordinated azo functionalities. This also reemphasised the concept of the coordination-induced lengthening of the azo bond of abim (∼1.30 Å), via dπ(CuI) → π*(azo, abim) back-bonding, with reference to its non-coordinating counterpart (1.265(6) Å).

Radical versus Nonradical States of Azobis(benzothiazole) as a Function of Ancillary Ligands on Selective Ruthenium Platforms.

The paper deals with the electronic impact of ancillary ligands on the varying redox features of azobis(benzothiazole) (abbt) in the newly introduced mononuclear ruthenium complexes [Ru(pap)2(abbt)]n (1n) and [Ru(bpy)2(abbt)]n (2n), where pap = 2-phenylazopyridine and bpy = 2,2'-bipyridine. In this regard, the complexes [RuII(pap)2(abbt•-)]ClO4 ([1]ClO4), [RuII(pap)2(abbt0)](ClO4)2 ([1](ClO4)2), [RuII(bpy)2(abbt0)](ClO4)2 ([2](ClO4)2), and [RuII(bpy)2(abbt•-)]ClO4 ([2]ClO4) were structurally and spectroscopically characterized. Unambiguous assignments of the aforestated radical and nonradical forms of abbt in 1+/2+ and 12+/22+, respectively, were made primarily based on their redox-sensitive azo (N═N) bond distances as well as by their characteristic electron paramagnetic resonance (EPR)/NMR signatures. Although the radical form of abbt•- was isolated as an exclusive product in the case of strongly π-acidic pap-derived 1+, the corresponding moderately π-acidic bpy ancillary ligand primarily delivered an oxidized form of abbt0 in 22+, along with the radical form in 2+ as a minor (<10%) component. The oxidized abbt0-derived [1](ClO4)2 was, however, obtained via the chemical oxidation of [1]ClO4. Both 1+ and 22+ displayed multiple closed by reversible redox processes (one oxidation O1 and four successive reductions R1-R4) within the potential window of ±2.0 V versus saturated calomel electrode. The involvement of metal-, ligand-, or metal/ligand-based frontier molecular orbitals along the redox chain was assigned based on the combined experimental (structure, EPR, and spectroelectrochemisry) and theoretical [density functional theory (DFT): molecular orbitals, Mulliken spin densities/time-dependent DFT] investigations. It revealed primarily ligand (abbt/pap or bpy)-based redox activities, keeping the metal ion as a simple spectator. Moreover, frontier molecular orbital analysis corroborated the initial isolation of the radical and nonradical species for the pap-derived 1+ and bpy-derived 22+ as well as facile reduction of pap and abbt in 1+ and 2+, respectively.

Ruthenium-Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru-Ag Coordination Polymer and Its Enhanced Water-Splitting Feature.

This article deals with the development of the unprecedented redox-mediated heterometallic coordination polymer {[RuIII(acac)2(µ-bis-η1-N,η1-N-BTD)2AgI(ClO4)]ClO4}n (3) via the oxidation of the monomeric building block cis-[RuII(acac)2(η1-N-BTD)2] (1) by AgClO4 (BTD = exodentate 2,1,3-benzothiadiazole, acac = acetylacetonate). Monomeric cis-[RuII(acac)2(η1-N-BTD)2] (1) and [RuII(acac)2(η1-N-BTD)(CH3CN)] (2) were simultaneously obtained from the electron-deficient BTD heterocycle and the electron-rich metal precursor RuII(acac)2(CH3CN)2 in refluxing CH3CN. Molecular identities of 1-3 were authenticated by their single-crystal X-ray structures as well as by solution spectral features. These results also reflected the elusive trigonal-planar geometry of the Ag ion in Ru-Ag-derived polymeric 3. Ru(III) (S = 1/2)-derived 3 displayed metal-based anisotropic EPR with ⟨g⟩/Δg = 2.12/0.56 and paramagnetically shifted 1H NMR. Spectroelectrochemistry in combination with DFT/TD-DFT calculations of 1n and 2n (n = 1+, 0, 1-) determined a metal-based (RuII/RuIII) oxidation and BTD-based reduction (BTD/BTD•-). The drastic decrease in the emission intensity and quantum yield but insignificant change in the lifetime of 3 with respect to 1 could be addressed in terms of static quenching and/or a paramagnetism-induced phenomenon. A homogeneously dispersed dumbbell-shaped morphology and the particle diameter of 3 were established by microscopic (TEM-EDX/SEM) and DLS analysis, respectively. Moreover, the dynamic nature of polymeric 3 was highlighted by its degradation to the η1-N-BTD coordinated monomeric fragment 1, which could also be followed spectrophotometrically in polar protic EtOH. Interestingly, both monomeric 1 and polymeric 3 exhibited efficient electrocatalytic activity toward water oxidation processes (OER, HER) on immobilization on an FTO support, which also divulged the better intrinsic water oxidation activity of 3 in comparison to 1.

Metal-to-Ligand Charge Transfer Induced Valence Tautomeric Forms of Non-Innocent 2,2'-Azobis(benzothiazole) in Ruthenium Frameworks.

The impact of metal-to-ligand charge transfer towards the redox noninnocence of 2,2'-azobis(benzothiazole) (abbt) has been highlighted on coordination to {RuII (acac)2 } (acac=2,4-pentanedionato). It led to the authentication of a series of mononuclear and dinuclear complexes incorporating variable oxidation states of abbt (abbt0/.-/2- ). Mononuclear 1 was identified as [RuIII (abbt.- )], a MLCT excited state of [RuII (abbt)]. Dinuclear 2 was however recognized as two discrete redox isomers: (i) radical bridged mixed-valent meso-[Ru2.5 (µ-abbt.- )Ru2.5 ] (2a) and (ii) dianionic ligand bridged isovalent meso-[RuIII (µ-abbt2- )RuIII ] (2b), demonstrating unprecedented structural confirmation of valence tautomerism in azo-based ligand systems. A crystal structure of [2]ClO4 validated the formation of [RuIII (µ-abbt.- ) RuIII ]ClO4 . Analysis of electronic structural forms of 1 and 2 in accessible redox states via spectroelectrochemistry and DFT revealed their electron reservoir feature.

Ruthenium-Hydride Assisted Remarkable Diversity Towards Non-Spectator Feature of Benzodifuroxan.

The present article demonstrates that ruthenium-hydride [RuII (H)(Cl)(CO)(PPh3 )3 ] mediated diverse functionalization modes of benzodifuroxan (BDF) encompassing two furoxan rings. Hydride transfer from the metal precursor facilitated multiple cascade reactions involving unsymmetrical cleavage of the furoxan rings of BDF, leading to the one-pot formation of a series of ruthenium (II) coordinated functionalized ligands exhibiting bidentate κ2 -N,O, κ2 -N,N' and bis-bidentate µ-bis(κ2 -N,O) modes. Further, a moderately stable intermediate species was also encountered in the reaction sequence in which the transformed deoxygenated ligand coordinated to the metal ion via the rarely manifested furazan ring (κ2 -N,N'' mode). The products were authenticated by their single-crystal X-ray structures and other spectroscopic/analytical techniques. Redox non-innocence of the functionalized ligands in the complexes was illustrated by spectroelectrochemistry (cyclic voltammmetry, UV-Vis. and EPR) in conjunction with DFT/TD-DFT calculations. Mechanistic outline for the facile ring opening processes of BDF including interconversions of complexes (e. g. reductive ring opening) were also addressed.

Electronically Triggered Switchable Binding Modes of the C-Organonitroso (ArNO) Moiety on the {Ru(acac)2} Platform.

This work evaluated the switchable binding profile of the biochemically relevant and redox non-innocent C-organonitroso (ArNO) moiety with the selective {Ru(acac)2} (acac = acetylacetonate) metal fragment as a function of external stimuli, including the solvent medium (EtOH versus toluene) and aryl substituents (C6H5, p-OMe-C6H4, and p-Cl-C6H4) in the framework of ArNO. In this context, the reaction of ArNO (Ar = C6H5 or p-OMe-C6H4) with the metal precursor RuII(acac)2(CH3CN)2 in polar protic EtOH led to the formation of monomeric [RuII(acac)2(ArNOo)2] (1a or 1b) with η1-N-bonded terminal ArNOo and double-ArNOo-bridged dimeric [(acac)2RuII(µ-ArNOo)2RuII(acac)2], 2a or 2b, respectively. On the other hand, the use of p-Cl-substituted ArNO selectively yielded the corresponding dimeric 2c. However, the use of nonpolar toluene resulted in monomeric 1 irrespective of the nature of aryl substituents in ArNO. Molecular identities, including the redox state of ArNOo in 1 and 2, were authenticated by their single-crystal X-ray structures as well as by solution spectral features. Though monomeric 1 exhibited reversible one-electron oxidation and reduction processes, leading to the electron paramagnetic resonance active [RuIII(acac)2(ArNOo)2]+ (1+; S = 1/2) and [RuII(acac)2(ArNO•-)(ArNOo)]- (1•-; S = 1/2), respectively, redox states of dimeric 2 were found to be unstable on the electrolysis time scale. Interestingly, monomeric 1 underwent transformation to dimeric 2 in the presence of a strong reducing agent, hydrazine hydrate, and the reverse process, i.e., conversion of dimeric 2 to 1, took place under the influence of external coordinating agent ArNO. The detailed experimental exploration, including kinetic investigations related to 1 → 2 and 2 → 1 transformations, revealed that the electronic aspects of ArNO (redox non-innocence of ArNOo/•-, π-accepting and coordinating features of ArNOo) had facilitated its switchable binding event in combination with the {Ru(acac)2} metal fragment.

Solvent-Mediated Functionalization of Benzofuroxan on Electron-Rich Ruthenium Complex Platform.

An unprecedented reactivity profile of biochemically relevant R-benzofuroxan (R=H, Me, Cl), with high structural diversity and molecular complexity on a selective {Ru(acac)2 } (acac=acetylacetonate) platform, in conjugation with EtOH solvent mediation, is revealed. This led to the development of monomeric [RuIII (acac)2 (L1R )] (1 a-1 c; L1R =2-nitrosoanilido derivatives) and dimeric [{RuII (acac)2 }2 (L2R )] (2 a-2 b; L2R =(1E,2E)-N1 ,N2 -bis(2-nitrosophenyl)ethane-1,2-diimine derivatives) complexes in one pot with a change in the metal redox conditions. The functionalization of benzofuroxan in 1 and 2 implied in situ reduction of N=O to NH- in the former and solvent-assisted multiple N-C coupling in the latter. The aforesaid transformation processes were authenticated through structural elucidation of representative complexes, and evaluated by their spectroscopic/electrochemical features, along with C2 D5 OD labeling and monitoring of the impact of substituents (R) in the benzofuroxan framework on the product distribution process. The noninnocent potential of newly developed L1 and L2 in 1 and 2, respectively, was also probed by spectroelectrochemistry in combination with DFT calculations.