Role of anagostic interactions in cycloplatination of telluroethers: Synthesis and structural characterization

Kolay, Siddhartha; Kumar, Mukesh; Wadawale, Amey; Das, Dasarathi; Jain, Vimal K.

doi:10.1016/j.jorganchem.2015.05.062

Cited by 7 publications

(11 citation statements)

References 36 publications

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“…The NMR spectral data ( 1 H, 125 Te, and 195 Pt) for [PtCl 2 (TeArAr′) 2 ] and for 7 are in accord with those reported recently by us . The 1 H NMR spectra of 4 – 10 displayed resonances and peak multiplicities as expected.…”

Section: Resultssupporting

confidence: 88%

“…The ether soluble component was characterized by NMR spectroscopy as cycloplatinated complex [PtCl(TeMes 2 ){Te(Mes)CH 2 C 6 H 2 Me 2 }] ( 7 ) while the ether insoluble part contained [PtCl 2 (PhCN) 2 ] ( 1a ) and [Pt 2 Cl 2 (μ-Cl) 2 (TeMes 2 ) 2 ] ( 8 ) as confirmed by 125 Te and 195 Pt NMR spectroscopy. Recently we have described the formation of 7 from 3e in refluxing THF …”

Section: Resultsmentioning

confidence: 99%

“…To study cycloplatination of telluroether ligands, recently we have isolated [PtCl 2 (TeArAr′) 2 ] complexes by employing the reaction between an aqueous solution of K 2 PtCl 4 and telluroether in an acetone mixture (eq ). Since the separation of the final products from the biphasic reaction medium was a tedious process, we thought to employ a reaction route involving [PtCl 2 (PhCN) 2 ] (eq ) and telluroether in an organic solvent. While the reaction with simple telluroethers gave the desired products, as has been reported earlier, − to our surprise, with a bulky telluroether (e.g., TeMes 2 ) formation of other intermediate complexes could be detected by 125 Te NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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Platinum-Mediated Activation of Coordinated Organonitriles by Telluroethers in Tetrahydrofuran: Isolation, Structural Characterization, and Density Functional Theory Analysis of Intermediate Complexes

et al. 2015

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The reactions of [PtCl2(NCR)2] with telluroethers (ArAr'Te) in organic solvents have been investigated. The reactions in dichloromethane yield [PtCl2(TeArAr')2], while those in tetrahydrofuran (THF) give different products depending on the steric demands of the aryl groups on tellurium, the molarity of the reactants, and the reaction conditions. The reactions between [PtCl2(PhCN)2] and TeArAr' in 1:1 molar ratio at room temperature in THF yield several products, like [PtCl2(TeArAr')2] (Ar/Ar' = Ph/Ph, o-tol/Mes, Mes/Mes), [PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], and [PtCl2{NC(O)Ph(TeMes2)}2]. The reaction with TeMes2 in refluxing THF gave [PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}] and [PtCl(TeMes2){Te(Mes)CH2C6H2Me2}], depending on the duration of heating. Reaction of [PtCl2(PhCN)2] with TeArMes afforded [PtCl2(TeArMes)2] (Ar = Ph, o-tol, and Mes), the formation of which decreased with increasing steric demand of the Ar group, together with [PtCl2{NC(O)Ph(TeArMes)}2]. The telluroether in the latter binds to nitrogen, and tellurium exists in the formal oxidation state of +4 (from XPS). The tellurium in these complexes exhibits secondary interactions with platinum (J((195)Pt-(125)Te) = 309-347 Hz) and with the carbonyl oxygen. These complexes slowly dissociate in solution to give [PtCl2(TeMesAr){NC(O)Ph(TeMesAr)}], finally leading to the formation of [PtCl2(TeMesAr)2]. Molecular structures of trans-[PtCl2(PhCN){NC(O)Ph[TeMes(o-tol)]}], trans-[PtCl2{NC(O)Ph(TeMes2)}2], trans-[PtCl2{NC(Ph)C4H7O}{NC(O)Ph(TeMes2)}], trans-[PtCl2{NC(O)Ph[TeMes(o-tol)]}2], trans-[PtCl2(TeMes2){NC(O)Ph(TeMes2)}], trans-[PtCl2{NC(O)Me(TeMes2)}2], and [PtCl(Te-o-tol){NC(O)Ph}2] have been unambiguously established by single-crystal X-ray diffraction analyses. Density functional theory calculations for some of the complexes were performed, and geometrical parameters are in good agreement with the values obtained from X-ray analyses.

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Section: Resultssupporting

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Platinum-Mediated Activation of Coordinated Organonitriles by Telluroethers in Tetrahydrofuran: Isolation, Structural Characterization, and Density Functional Theory Analysis of Intermediate Complexes

et al. 2015

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“…The conversion of the cis to the trans form was encountered in the 125 TeNMR spectrum of the latter complexes, which exhibited a single resonance rst, but in the longer acquisition results two prominent resonances were observed, attributed to the cis as well as trans forms. 94 An agostic interaction between telluroethers and metal atoms has also been documented in these complexes, where a toluene-methanol solution of [ 109,110 These latter complexes are also isolated at room temperature by the precursor [M 3 (CO) 10 (MeCN) 2 ] (M ¼ Ru, Os). 113 While the reaction with 2 ], in which both tellurium linkages were at opposite Os-Os edges.…”

Section: Palladium and Platinummentioning

confidence: 98%

“…In the case of the latter ligand system, palladium is directly coordinated to all four nitrogen atoms. 92,93 An interesting example of a halobridged complex, [ [93][94][95] These complexes were formed due to the chlorobridged cleavage reaction with the substitution of thio and seleoether through monotellurides. Usually, telluroether complexes are oriented in the cis form, which is slowly transformed to the trans isomer in solution.…”

Section: Palladium and Platinummentioning

confidence: 99%