Synthesis and characterization of 1,1′-ferrocenyldichalcogenolato complexes of palladium and platinum

† Electronic Supplementary Information (ESI) available: Crystal data and details of structure determination and selected bond parameters of 2-5, CCDC 1522462-1522465, Definition of the angle of distortion. Energy profile of Th2Te2 + [Pt((h 2nb)(dppn)]. 31 P{ 1 H} NMR spectrum of [Pt(TeTh)2(dppn)].The oxidative addition reaction of ditellurides R2Te2 [R = n Bu, Ph, Th (2-thienyl, C4H3S)] to [Pt(η 2 -nb)(dppn)] (nb = norbornene, dppn = 1,2-bis(diphenylphosphino)naphthalene) was found to afford [Pt(TeR)2(dppn)] [R = n Bu (1), Ph (2), Th (3)] and [Pt(TeR)(R)(dppn)] [R = Ph (4), Th (5)] as a result of the cleavage of the Te-Te or C-Te bond, respectively. The reactions and the product distributions were monitored by 31 P{ 1 H} NMR spectroscopy. The spectral interpretation was assisted by the high-yield preparation of [Pt(TePh)2(dppn)] (2) and [Pt(TeTh)2(dppn)] (3) by ligand echange reactions from [PtCl2(dppn)], and by the crystal structure determinations and spectral characterizations of 2 and 3. Two series of reactions were carried out both at room temperature and at -80 o C. One involved the addition of the toluene solution of R2Te2 to that of [Pt(η 2 -nb)(dppn)], and the other the addition of [Pt(η 2 -nb)(dppn)] solution to the R2Te2 solution. The oxidative addition of n Bu2Te2 to [Pt(η 2 -nb)(dppn)] yielded solely [Pt(Te n Bu)2(dppn)]. In case of Ph2Te2 and Th2Te2, the reaction of equimolar amounts of ditelluride and [Pt(η 2 -nb)(dppn)] afforded only [Pt(TeR)(R)(dppn)] (R = Ph, Th), but when an excess of R2Te2 was used, the addition of [Pt(η 2 -nb)(dppn)] to the ditelluride resulted in the formation of a mixture of [Pt(TeR)2(dppn)] and [Pt(TeR)(R)(dppn)] with the latter the main component. An excess of R2Te2 and the lowering of the temperature favoured the formation of [Pt(TeR)2(dppn)]. The reaction energetics in toluene was calculated at revPBE GGA DFT / TZVP(f) level of theory. The increase of the electron withdrawing nature of the organic substituent rendered [Pt(TeR)(R)(dppn)] increasingly stable with respect to [Pt(TeR)2(dppn)]. The computation of the energy profiles of the likely pathways of the oxidative addition indicated that concurrent formation of [Pt(TeR)2(dppn)] and [Pt(TeR)(R)(dppn)] (R = Ph, Th) may be more likely than the formation of the latter due to the decomposition of the former. This was verified experimentally by stirring pure [Pt(TeR)2(dppn)] in toluene for a prolonged time at room tempertature. No decomposition was observed.

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Recent advances in computational liquid-phase ⁷⁷Se NMR

Krivdin¹

2021

Russ. Chem. Rev.

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This review aims to highlight significant progress in the calculation of 77Se NMR chemical shifts and spin – spin coupling constants involving selenium substantiated with a vast amount of experimental data. The material is arranged in two basic sections: the first one dealing with the calculation of 77Se NMR chemical shifts and the second one dealing with the computation of spin – spin coupling constants involving 77Se nucleus, namely 77Se–1H, 77Se–13C and 77Se–77Se together with some more exotic types of couplings, 77Se – 15N, 77Se–19F, 77Se–29Si and 77Se–31P. A special attention is focused on the stereoelectronic effects involving selenium atom and their manifestation in the 77Se NMR spectra of organoselenium compounds studied with the aid of the modern calculation of 77Se NMR parametres in combination with experimental results. The bibliography includes 114 references.

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Synthesis and characterization of 1,1′-ferrocenyldichalcogenolato complexes of palladium and platinum

Cited by 3 publications

References 34 publications

Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

Recent advances in computational liquid-phase ⁷⁷Se NMR

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Synthesis and characterization of 1,1′-ferrocenyldichalcogenolato complexes of palladium and platinum

Cited by 3 publications

References 34 publications

Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

Recent advances in computational liquid-phase 77Se NMR

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Product

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Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M = Pd, pt; dppf = bis(diphenylphisphino)ferrocene)

Recent advances in computational liquid-phase ⁷⁷Se NMR