Azo-oximate metal-carbonyl to metallocarboxylic acid <i>via</i> the intermediate Ir(<scp>iii</scp>) radical congener: quest for co-ligand driven stability of open- and closed-shell complexes

Dinda, Soumitra; Pramanik, Shuvam; Basu, Jaydeep; Patra, Sarat Chandra; Ganguly, Sanjib

doi:10.1039/d2dt00345g

Cited by 6 publications

(2 citation statements)

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“…Our group has been striving to comprehend the role of ancillary ligands in influencing the stereoselectivity of C–H bond activation by using platinum group metal complexes. − In this article we have presented how judicious choice of coligands can induce selectivity in M–Cl (M = Ru II , Rh III ) bond activation via the formation of halogen bond (XB). The ligand, 2-pyridylhydrazinophenanthrenequinone, HL PyHPQ 1 was used to synthesize two isomeric complexes trans- and cis- [Ru II L PyHPQ (CO)(PPh 3 )Cl] 2 and 3 respectively and in both cases the ligand exhibits tridentate behavior.…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)

Dinda,

Jana,

Gomila

et al. 2024

Crystal Growth & Design

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The isolation of isomeric complexes trans-[Ru II L PyHPQ (CO)(PPh 3 )Cl] 2 and cis-[Ru II L PyHPQ (CO)(PPh 3 )Cl] 3, (Cl and PPh 3 are trans in 2 and they are cis in 3 respectively) as well as [Ru II L PyHPQ (CO)(PPh 3 ) 2 Cl] 4 and [Rh III L PyHPQ (PPh 3 )Cl 2 ] 5 disclose the flexidentate nature of the multifunctional ligand, HL PyHPQ 2-pyridylhydrazinophenanthrenequinone, 1. These complexes are maneuvered as molecular templates for understanding the role of halogen bonds (XB) in M−Cl bond activation and subsequent cleavage processes. Both isomeric forms 2 and 3 furnish trans-[Ru II L PyHPQ (CO)(PPh 3 )(I 3 )] 6 (where PPh 3 and I 3 − in trans position) when they are treated separately with I 2 in a hydrocarbon solvent. Nonetheless, complex 5 is converted to 7 upon similar treatment but 4 remains unreacted. Crystal structure of 7 revealed that it is composed of 62% trans-[Rh III L PyHPQ (PPh 3 )Cl(I 3 )] and 38% trans-[Rh III L PyHPQ (PPh 3 )Cl(ClI 2 )] (where PPh 3 and I 3 − /ClI 2 − are trans). The I 3 − /ClI 2 − gets coordinated to metal centers exclusively in an end-on fashion in all cases. Since the valence state of metal centers remains unaltered in due course of the reaction, the emergence of M−I 3 /M−ClI 2 from M−Cl in the absence of any reductant in solution is indicative of prior activation of M−Cl bond via the formation of Halogen Bond (XB) of type [M−Cl−I−I] in an intermediate step. The geometrical fluctuations around the coordination sphere during the transformation of cis-[Ru II L PyHPQ (CO)(PPh 3)Cl] 3 to trans-[Ru II L PyHPQ (CO)(PPh 3 )(I 3 )] 6 is reminiscent of the active influence of XB, triggering the isomerization of 3 to 2 owing to steric encumbrance, before it is being converted to 6. Electrochemical behavior and optoelectronic properties of the complexes have been complimented by theoretical analysis and the structures were characterized by SCXRD. Repeated π-stacking motifs in the crystalline phase architecture of the complexes have been scrutinized using DFT calculations.

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Section: Introductionmentioning

confidence: 99%

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)

Dinda,

Jana,

Gomila

et al. 2024

Crystal Growth & Design

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“…50–83 Also, the electron acceptor ability of these ligands may be influenced by ancillary ligands and this property has been exploited in metal mediated organic synthesis. 84–86 These complexes are also utilized as molecular memory switching devices and comprehending their voltage-induced current characteristics. 87,88 Besides these, the azo-chromophore exhibits varied geometrical ( Z / E isomerization) as well as electronic structures on photoinduction 89 and can form mesogenic films or polymers 90,91 when modified appropriately.…”

Section: Introductionmentioning

confidence: 99%

Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective

Swatiputra,

Mukherjee,

Dinda

et al. 2023

Dalton Trans.

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Molecular and Electronic Structures, Spectra, Electrochemistry and Anti‐bacterial Efficacy of Novel Heterocyclic Hydrazones of Phenanthrenequinone and Their Nickel(II) Complexes

et al. 2022

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A pair of tridentate ligands incorporating heterocyclic hydrazones of 9,10‐phenanthrenequinone viz,. pyridyl‐hydrazino‐phenathrenequinone HLPy 1a and benzothiazolyl‐hydrazino‐phenathrenequinone HLBenz 1b have been synthesized and both behave as monoanionic towards nickel(II), forming meridional octahedral complexes of type [Ni(LPy)2] 2a and [Ni(LBenz)2] 2b as evident from single crystal X‐ray diffraction studies. The complexes are electro‐active in solution and nature of redox orbitals has been analysed by theoretical means. They display two oxidative and two reductive responses that have been ascribed to the redox processes of coordinated ligands. The electronic absorption spectral patterns of two complexes are analogous barring the fact that lower energy transition for 2b is marginally bathochromically shifted relative to that of 2a and it has been clarified by TD‐DFT studies. Anti‐bacterial efficacy of the ligands HLPy 1a, HLBenz 1b and complexes [Ni(LPy)2] 2a, [Ni(LBenz)2] 2b against four Gram‐positive and four Gram‐negative strains has been explored. [Ni(LPy)2] 2a exhibits more pronounced efficacy than [Ni(LBenz)2] 2b and these are greater than those of the corresponding ligands. The mode of action of 2a is essential via DNA damage while protein leakage and membrane lipid damage were observed upon treatment with 2b.

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Azo-oximate metal-carbonyl to metallocarboxylic acid via the intermediate Ir(iii) radical congener: quest for co-ligand driven stability of open- and closed-shell complexes

Abstract: Radical-mediated conversion of metal carbonyl to metallocarboxylic acid has been successfully accomplished along with the exploration of the stability of open- and closed-shell complexes by stereochemical alteration of co-ligands.

Cited by 6 publications

References 123 publications

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)

Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective

Molecular and Electronic Structures, Spectra, Electrochemistry and Anti‐bacterial Efficacy of Novel Heterocyclic Hydrazones of Phenanthrenequinone and Their Nickel(II) Complexes

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Azo-oximate metal-carbonyl to metallocarboxylic acid via the intermediate Ir(iii) radical congener: quest for co-ligand driven stability of open- and closed-shell complexes

Abstract: Radical-mediated conversion of metal carbonyl to metallocarboxylic acid has been successfully accomplished along with the exploration of the stability of open- and closed-shell complexes by stereochemical alteration of co-ligands.

Cited by 6 publications

References 123 publications

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I3)

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I3)

Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective

Molecular and Electronic Structures, Spectra, Electrochemistry and Anti‐bacterial Efficacy of Novel Heterocyclic Hydrazones of Phenanthrenequinone and Their Nickel(II) Complexes

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Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)

Halogen Bonding in Stereoselective Metal Chloride (M–Cl) Bond Activation and Transformation to Metal Triiodide (M–I₃)