4-Membered metallodithiophosphinate rings – flat or puckered? A comparison of two crystal structures with computational and literature data

Esterhuysen, Catharine; Kruger, Gert J.; Blewett, Gavin; Raubenheimer, Helgard G.

doi:10.1016/j.ica.2005.10.006

Cited by 8 publications

(3 citation statements)

References 15 publications

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“…For 1 , this four-membered metallocycle is planar, but for 2 and 3 the phosphorus atom is puckered out of the NiS 4 plane by 0.18 Å and 0.39 Å, respectively. Analogous puckering is common in the solid-state structures of many diaryldithiophosphinates and has been attributed to intermolecular π–π van der Waals interactions . Consistent with this analysis, inspection of the extended crystal structures shows no obvious intermolecular interactions for 1 but does reveal a possibility for intermolecular aryl π–π stacking interactions for 2 and 3 (Figure S2, Supporting Information).…”

Section: Resultssupporting

confidence: 71%

“…Analogous puckering is common in the solid-state structures of many diaryldithiophosphinates and has been attributed to intermolecular π−π van der Waals interactions. 50 Consistent with this analysis, inspection of the extended crystal structures shows no obvious intermolecular interactions for 1 but does reveal a possibility for intermolecular aryl π−π stacking interactions for 2 and 3 (Figure S2, Supporting Information). The observed π−π overlap in the structures of 2 and 3 appears to be accommodated by free rotation of the aryl groups around the P−C bond.…”

Section: ■ Introductionsupporting

confidence: 69%

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Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

et al. 2012

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A method to evaluate the electronic structure of minor actinide extractants is described. A series of compounds containing effective and ineffective actinide extractants (dithiophosphinates, S(2)PR(2)(-)) bound to a common transition metal ion (Ni(2+)) was analyzed by structural, spectroscopic, and theoretical methods. By using a single transition metal that provides structurally similar compounds, the metal contributions to bonding are essentially held constant so that subtle electronic variations associated with the extracting ligand can be probed using UV-vis spectroscopy. By comparison, it is difficult to obtain similar information using analogous techniques with minor actinide and lanthanide complexes. Here, we demonstrate that this approach, supplemented with ground state and time-dependent density functional theory, provides insight for understanding why high separation factors are reported for the extractant HS(2)P(o-CF(3)C(6)H(4))(2), while lower values are reported and anticipated for other HS(2)PR(2) derivatives (R = C(6)H(5), p-CF(3)C(6)H(4), m-CF(3)C(6)H(4)). The implications of these results for correlating electronic structure with the selectivity of HS(2)PR(2) extractants are discussed.

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Section: Resultssupporting

confidence: 71%

Section: ■ Introductionsupporting

confidence: 69%

Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

et al. 2012

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“…It has been shown that dithiophosphorus ligands are exceptional for this extraction as they are classified as soft-donor species [7][8][9][10][11][12][13][14]. Furthermore, dithiophosphorus ligands can be coordinated to the main group and transition metals, in particular, with soft metal centers such as palladium(II) and copper(I) [15,16]. DTPs are common bidentate ligands that can create stable complexes with soft acid type cations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural characterization of Pd(II) and Cu(I) complexes containing dithiophosphorus ligand and their catalytic activities for Heck reaction

et al. 2016

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2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson's reagent) was made to react with benzylamine to produce [(PhCH2NH)(p-C6H4OMe)PS2] -[PhCH2NH3] + in a very facile manner. From the abovementioned product, two new complexes {Pd[(PhCH2NH)(p-C6H4OMe)PS2]2} (C1) and {Cu2(PPh3)2[(PhCH2NH)(p-C6H4OMe)PS2]2} (C2) were obtained in high yields whose molecular structures were ascertained by X-ray diffraction analysis, IR and NMR spectroscopy, and elemental analysis. The catalytic properties of both complexes were evaluated in the Heck reaction. High turnover numbers (TONs) and yields were observed for palladium catalyst and It was revealed that dicopper(I) complex by a distance of 2.84 Å between metal ions, bearing triphenylphosphine and dithiophosphorus ligands, can catalyze the Heck reaction. This is the first report of Cu(I) complex as catalyst in the Heck reaction. Natural bonding orbital (NBO) analysis for C1 indicated that natural charge on Pd atom is -0.07e and Pd atom has formed four sigma bonds with S atoms. Similarly, NBO analysis revealed no significant Cu…Cu interaction in dicopper complex C2.

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Dithiophosphorus‐Palladium Complexes as a Catalyst in the Heck Reaction via Pd(II)/Pd(IV) Catalytic Cycle: A Combined Experimental and Computational Study

et al. 2018

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The palladium-catalyzed Heck reaction is the most effective method for vinylation of unsaturated halides. Here, new thermally stable palladium(II) complexes {(4OMeÀPh) RPS 2 } 2 Pd [R = C 5 H 11 NH (1); R = CH 3 CH 2 NHCH 3 (2); R=OCH 3 (3)] were readily synthesized in a high yield by the reaction of PdCl 2 with dithiophosphorus ligands. The molecular structures of 1 and 2 were determined by means of X-ray diffraction analysis. The catalytic activity of all complexes was evaluated in Heck reaction. The results revealed that the complexes are highly active catalysts in coupling of aryl bromides with styrene. The Hammett plot of the competition experiments of various aryl bromides with styrene, catalyzed by the complexes, displayed very good linear correlation with a positive slope (1) within a range of 3.99-4.39 for 1-3. The absence of any decomposition signs together with negative Hg-poisoning tests indicated that the liberation of Pd(0) species in the catalytic cycle is unlikely. So, it was supposed that the palladium(II)-catalyzed Heck reaction might not proceed via classical Pd(0)/Pd(II) catalytic cycle. To find the most probable mechanism, density functional theory calculations were performed and the predicted data compared with the experimental results. Upon the obtained results, the Pd(II)/Pd(IV) catalytic cycle was proposed as the most plausible mechanism. The overall free energy profile showed that the first step of the mechanism (oxidative addition) with a free energy barrier of 33.8 kcal/mol involves the highest energy barrier and can be considered as the rate determining step of the mechanism.

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4-Membered metallodithiophosphinate rings – flat or puckered? A comparison of two crystal structures with computational and literature data

Cited by 8 publications

References 15 publications

Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

Synthesis and structural characterization of Pd(II) and Cu(I) complexes containing dithiophosphorus ligand and their catalytic activities for Heck reaction

Dithiophosphorus‐Palladium Complexes as a Catalyst in the Heck Reaction via Pd(II)/Pd(IV) Catalytic Cycle: A Combined Experimental and Computational Study

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4-Membered metallodithiophosphinate rings – flat or puckered? A comparison of two crystal structures with computational and literature data

Cited by 8 publications

References 15 publications

Probing Ni[S2PR2]2 Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

Probing Ni[S2PR2]2 Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

Synthesis and structural characterization of Pd(II) and Cu(I) complexes containing dithiophosphorus ligand and their catalytic activities for Heck reaction

Dithiophosphorus‐Palladium Complexes as a Catalyst in the Heck Reaction via Pd(II)/Pd(IV) Catalytic Cycle: A Combined Experimental and Computational Study

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Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry

Probing Ni[S₂PR₂]₂ Electronic Structure to Generate Insight Relevant to Minor Actinide Extraction Chemistry