Cleavage of RuC(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: Spectroscopic, structural and computational studies

Ghosh, M. K.; Mallick, Suman; Islam, Anikul; Mohapatra, Sudip; Chattopadhyay, Swarup

doi:10.1016/j.poly.2015.11.040

Cited by 8 publications

(3 citation statements)

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“…Specific compounds will be identified by putting R in the parenthesis e. g. 2 (Me) stands for [Ru(PPh 3 )( η 2 ‐MeL)(CO)( μ ‐ p ‐ClC 6 H 4 S)] 2. Although in the present case, the reason behind the Ru—C(aryl) bond cleavage of 1 is not clear but this phenomenon has already been observed in the reactions of complex 1 with 2‐mercaptopyrimidine and pyridine‐2,6‐dicarboxylate ligands . Effort to synthesize the complex 2 by reacting the Schiff mono base of 4‐methyl‐2,6‐diformylphenol with Ru(PPh 3 ) 3 Cl 2 in presence of sodium p‐chlorothiophenolate has failed.…”

Section: Resultsmentioning

confidence: 74%

“…Despite the extensive reaction chemistry of 1 , the reactivity of complex 1 with thiolato ligand has not yet been explored. Our interests in ruthenium chemistry, led us to investigate the reaction of 1 with thiolato ligand. We are interested in synthesizing the dinuclear ruthenium complexes by utilizing the bridging nature of the thiolato ligand.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium‐Carbon(Aryl) Bond Cleavage and Change in the Ligand Coordination Mode in a Four‐Membered Ortho‐Metalated Ruthenium(II) Organometallics Promoted by Thiolato Ligands

et al. 2017

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The reaction of Ru(η2‐RL)(PPh3)2(CO)Cl [η2‐RL is C6H2O‐2‐CHNHC6H4R(p)‐3‐Me‐5 and R=Me, OMe, Cl] with excess sodium p‐chlorothiophenolate (p‐ClC6H4SNa) in dichloromethane–tetrahydrofuran medium afforded the binuclear complexes of the type [Ru(PPh3)(η2‐RL)(CO)(p‐ClC6H4S)]2 [η2‐RL is C6H3O‐2‐CHNC6H4R(p)‐3‐Me‐5] in excellent yield. The binding of the thiolato ligands is attended with the cleavage of the Ru–C(aryl) and Ru–Cl bonds in Ru(η2‐RL)(PPh3)2(CO)Cl and the RL ligands are now coordinated with the metals in [Ru(PPh3)(η2‐RL)(CO)(p‐ClC6H4S)]2 via the imine nitrogen and the phenolato oxygen atoms. The CO ligand in [Ru(PPh3)(η2‐RL)(CO)(p‐ClC6H4S)]2 remains trans to the phenolato function as in Ru(η2‐RL)(PPh3)2(CO)Cl. The spectral (UV‐vis, IR, NMR, mass) and electrochemical data of the complexes are included. In dichloromethane solution the complexes display two successive one‐electron oxidation waves. The comproportionation constants (KC) as calculated by the ▵E1/2 values of the complexes are in the order of 105 indicating that the two metal centers in [Ru(PPh3)(η2‐RL)(CO)(p‐ClC6H4S)]2 are only weakly coupled by the bridging thiolato liagnds. Structure determinations of [Ru(PPh3)(η2‐RL)(CO)(p‐ClC6H4S)]2 (R=Me, OMe) have revealed a distorted octahedral RuCONPS2 coordination sphere with the pairs (P, S), (C, O), and (N, S) defining the three trans directions. The Ru⋅⋅⋅⋅Ru distances in the complexes are clearly outside of the range for a Ru‐Ru single bond. The electronic structures and the absorption spectra of the complexes are also scrutinized by the density functional theory (DFT) and Time‐dependent DFT analysis.

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Section: Resultsmentioning

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Ruthenium‐Carbon(Aryl) Bond Cleavage and Change in the Ligand Coordination Mode in a Four‐Membered Ortho‐Metalated Ruthenium(II) Organometallics Promoted by Thiolato Ligands

et al. 2017

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“…The coordination of hpbt ligand to Ru1 center results in the distortion of the equatorial angles around the central ruthenium atom in such a way that the four equatorial angles differ containing Ru(II) complexes[4c,31]. Ru-Cl1 and Ru-C50 bond distances fall in the range observed in other structurally characterized ruthenium complexes[19,32].…”

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confidence: 99%

Benzothiazole and benzoxazole promoted cleavage of Ru − C(aryl) bond in a four-membered ortho-metalated ruthenium(II) organometallics

Chowdhury

Ghosh²,

Garu³

et al. 2023

Struct Chem

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The four-membered ruthenium(II) organometallics Ru(η 2 -RL)(PPh 3 ) 2 (CO)(Cl) (1) where η 2 -RL = C 6 H 2 O-2-CHNHC 6 H 4 R(p)-3-Me-5 and R = CH 3 reacts with 2-(2-hydroxyphenyl)benzothiazole (Hhpbt) and 2-(2hydroxyphenyl)benzoxazole (Hhpbo) in re uxing ethanol to afford Ru(PPh 3 ) 2 (CO)(hpbt)Cl (2) and Ru(PPh 3 ) 2 (CO)(hpbo)Cl (3) respectively in excellent yield. In the course of these reactions the Ru-C(aryl) bond in 1 is cleaved and the RL ligand is no longer coordinated with the metal center in the products. The spectral (UV-vis, IR, 1 H NMR) and electrochemical data of the complexes are reported. The identity of complex 2 has been established by single-crystal X-ray structure determination. The electronic structure and the absorption spectra of the complexes are scrutinized by DFT and TD-DFT analyses.

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The first examples of nitrobenzoate coordinated ruthenium(II) organometallics: reaction conditions driven product formation

Chowdhury,

Garu,

Mondal

et al. 2024

Struct Chem

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Cleavage of RuC(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: Spectroscopic, structural and computational studies

Cited by 8 publications

References 50 publications

Ruthenium‐Carbon(Aryl) Bond Cleavage and Change in the Ligand Coordination Mode in a Four‐Membered Ortho‐Metalated Ruthenium(II) Organometallics Promoted by Thiolato Ligands

Ruthenium‐Carbon(Aryl) Bond Cleavage and Change in the Ligand Coordination Mode in a Four‐Membered Ortho‐Metalated Ruthenium(II) Organometallics Promoted by Thiolato Ligands

Benzothiazole and benzoxazole promoted cleavage of Ru − C(aryl) bond in a four-membered ortho-metalated ruthenium(II) organometallics

The first examples of nitrobenzoate coordinated ruthenium(II) organometallics: reaction conditions driven product formation

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