Supramolecular 3‐/4‐Mercaptobenzoic Acid Complexes of Palladium(II) and Platinum(II) Stabilized by Hydrogen Bonding

Vivekananda, K. V.; Dey, Sandip; Wadawale, Amey; Bhuvanesh, Nattamai; Jain, Vimal K.

doi:10.1002/ejic.201301562

Cited by 11 publications

(8 citation statements)

References 55 publications

(50 reference statements)

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“…The 1 J Pt–P values of platinum complexes (2833–2912 Hz) are significantly reduced as compared to subunit 2b (∼3704 Hz) due to two strong trans influencing thiolate groups . All the Pt nuclei are magnetically equivalent, as a triplet in 195 Pt NMR spectra for 3b and 4b (see Figure S15 in the Supporting Information) is observed due to coupling with two equivalent 31 P nuclei.…”

Section: Resultsmentioning

confidence: 96%

“…14,24 The 1 J Pt−P values of platinum complexes (2833−2912 Hz) are significantly reduced as compared to subunit 2b (∼3704 Hz) due to two strong trans influencing thiolate groups. 18 All the Pt nuclei are magnetically equivalent, as a triplet in 195 Pt NMR spectra for 3b and 4b (see Figure S15 in the Supporting The above complexes were also crystallized from the reactions of 1 and 2 when performed in 1:1 ratio showing the formation of identical products. This is confirmed by the experiments involving stepwise addition of ligand to metal ( Figure 1) and metal to ligand (see Figure S16 in the Supporting Information) employing 2a and 1c.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

“…Using carboxylic acid as another group the S-based mercaptobenzoic acid ligands have been employed to construct supramolecular structures of tin and gold complexes via aurophilic and hydrogen-bonding interactions. The supramolecular assemblies of Pd(II) and Pt(II) complexes derived from mercaptobenzoic acid via intermolecular H-bonding have been recently synthesized by us . The flexible and hemilabile heteroligands containing phosphine and chalcogen (S, Se) groups are also used for the synthesis of palladium and platinum macrocyclic structures via weak-link approach, whereas the ligands containing two S donor atoms symmetrically separated by a rigid aromatic core (Scheme ) have not been explored as building blocks to prepare functional SCCs of Pd and Pt.…”

Section: Introductionmentioning

confidence: 99%

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Supramolecular Macrocyclic Pd(II) and Pt(II) Squares and Rectangles with Aryldithiolate Ligands and their Excellent Catalytic Activity in Suzuki C–C Coupling Reaction

et al. 2015

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Addition of 1,4-benezenedithiol and 4,4'-biphenyldithiol to M(OTf)2 (M = cis-[Pt(PEt3)2](2+) or cis-[Pd(dppe)](2+)) (dppe = 1,2-bis(diphenylphosphino)ethane) gave self-assembled tetranuclear complexes [M2{S(C6H4)nS}]2(OTf)4 (n = 1, 2). The same reaction with 1,4-benezenedimethanethiol yielded octanuclear supramolecular coordination complexes (SCC) [M2{SCH2C6H4CH2S}]4(OTf)8. These complexes were characterized by NMR, mass, and UV-vis spectroscopies, cyclic voltammetry, as well as density functional theory studies and represent the first examples of SCCs constructed by thiolate groups and square-planar metal ions. The rectangular shape of tetranuclear complexes and square shape of octanuclear complex are confirmed by single-crystal structures and computational studies. The palladium complexes showed excellent catalytic activity in Suzuki C-C cross-coupling reactions with high turnover numbers (2 × 10(7)), even with low catalyst loading.

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Section: Resultsmentioning

confidence: 96%

Section: Inorganic Chemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Supramolecular Macrocyclic Pd(II) and Pt(II) Squares and Rectangles with Aryldithiolate Ligands and their Excellent Catalytic Activity in Suzuki C–C Coupling Reaction

et al. 2015

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“…It may be due to the tendency of the ligand to form sparingly soluble oligomer or polymer rather than the discrete molecules. We have recently reported the supramolecular assemblies of Pd(II) and Pt(II) complexes using mercaptobenzoic acid via intermolecular H-bonding and aryl dithiolate ligands via coordinate bond. The macrocyclic palladium complexes, [Pd 2 (dppe) 2 {S(C 6 H 4 ) n S}] 2 (OTf) 4 and [Pd 2 (dppe) 2 (SCH 2 C 6 H 4 CH 2 S)] 4 (OTf) 8 ( n = 1, 2; dppe = 1,2-bis(diphenylphosphino)ethane) showed excellent catalytic activity in Suzuki and Heck C–C coupling reactions.…”

Section: Introductionmentioning

confidence: 99%

Xantphos-Capped Pd(II) and Pt(II) Macrocycles of Aryldithiolates: Structural Variation and Catalysis in C–C Coupling Reaction

et al. 2019

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The self-assembly of Xantphos-capped M(OTf)2 (M = cis-[M′(Xantphos)]2+; M′ = Pd, Pt) with bridging ligands 1,4-benezenedithiol or 4,4′-biphenyldithiol has been investigated. The reactions have yielded complexes [M{S(C6H4) n SH}]2(OTf)2 (I) and [M 2{S(C6H4) n S}]2(OTf)4 (II) (n = 1 or 2). The equilibrium between I and II has been established in platinum complexes for n = 2, whereas the analogous Pd complex exclusively exist as II. These results are different from our previously reported dppe or triethyl phosphine-capped complexes which showed only type II. The same reaction with 1,3-benezenedithiol lead to the complex [M 2(SC6H4SSC6H4S)](OTf)2 (III), containing a S–S bond between two thiolate ligands, formed via a complex of type I in solution. Characterization of the complexes was accomplished by NMR spectroscopy, UV–vis spectroscopy and mass spectrometry, and X-ray crystallography. Density functional calculations were performed to estimate the relative stability of three types of complexes. The palladium complexes are excellent catalysts in Suzuki C–C cross coupling reactions under mild conditions, and can be reused eight times without losing significant yield. The activity of the Pd catalysts derived from three dithiol ligand follows opposite trend of the stability as III > II > I. The comparative catalytic activity of the tetranuclear Pd complexes (II) of bis-phosphines of varied bite angles, including the structurally characterized [Pd2(dppf)2(SC12H8S)]2(OTf)4 has also been demonstrated.

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“…There are several inter‐ and intramolecular hydrogen bonding interactions involving water molecules. An intramolecular H‐bonding exist between the coordinated H 2 O and triflate ions; the typical donor (D: oxygen)⋅⋅⋅acceptor (A: oxygen atom) distances such as D–H, H⋅⋅⋅A and D⋅⋅⋅A are 0.86, 1.91 and 2.75 Å, respectively . The molecules of 2 are associated via intermolecular H‐bonding through coordinated H 2 O⋅⋅⋅triflate (counter ion)⋅⋅⋅H 2 O (solvated)⋅⋅⋅H 2 O coordinated to another molecule.…”

Section: Resultsmentioning

confidence: 99%

Coordination Polymers of Palladium Bridged by Carboxylate and Dimethylaminoalkylselenolate Ligands

Paluru

Dey

Wadawale

et al. 2015

Chemistry An Asian Journal

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Coordination polymers of palladium stabilized by dimethylaminoalkylselenolate and carboxylate ligands are reported. The reaction of [PdCl(SeCH2 CH2 NMe2 )]3 with AgOTf followed by treatment with sodium acetate afforded [Pd(0) Pd(II) 4 (SeCH2 CH2 NMe2 )3 (OAc)3 ](OTf)2 (1) in which one of the Pd atoms is in the zero oxidation state. In the absence of NaOAc, a tetranuclear complex, [Pd(II) 4 (SeCH2 CH2 NMe2 )4 (OTf)](OTf)3 (2), is isolated from the same reaction. Subsequent treatment with NaO2 CR afforded [Pd4 (SeCH2 CH2 NMe2 )4 (O2 CR)4 ] (R=tBu (3) and Ph (4)). The reaction of [PdCl(SeCH2 CH2 CH2 NMe2 )]2 with AgOTf and NaOAc yielded an ionic binuclear complex, [Pd(II) 2 (SeCH2 CH2 CH2 NMe2 )2 (OAc)](OTf) (5). These complexes have been characterized by NMR spectroscopy, crystal structures, and in some cases by X-ray photoelectron spectroscopy, cyclic voltammetry and mass spectrometry. Complexes 1 and 5 are associated through secondary interactions and coordinate bonds, respectively, to generate polymeric structures in the solid state.

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Supramolecular 3‐/4‐Mercaptobenzoic Acid Complexes of Palladium(II) and Platinum(II) Stabilized by Hydrogen Bonding

Cited by 11 publications

References 55 publications

Supramolecular Macrocyclic Pd(II) and Pt(II) Squares and Rectangles with Aryldithiolate Ligands and their Excellent Catalytic Activity in Suzuki C–C Coupling Reaction

Supramolecular Macrocyclic Pd(II) and Pt(II) Squares and Rectangles with Aryldithiolate Ligands and their Excellent Catalytic Activity in Suzuki C–C Coupling Reaction

Xantphos-Capped Pd(II) and Pt(II) Macrocycles of Aryldithiolates: Structural Variation and Catalysis in C–C Coupling Reaction

Coordination Polymers of Palladium Bridged by Carboxylate and Dimethylaminoalkylselenolate Ligands

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