Versatile routes to selenoether functionalised tertiary phosphines

Cunningham, Tom J.; Elsegood, Mark R. J.; Kelly, Paul F.; Smith, Martin B.; Staniland, Paul M.

doi:10.1039/c0dt00004c

Cited by 13 publications

(6 citation statements)

References 35 publications

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“…This self-assembled dimer is reinforced by Pt⋯Pt interactions that are separated by 3.332 Å. Interestingly, the fully optimized structure of this dimer agrees well with the experimental one (see Table S2 in the ESI† for more details). Refcode PUYWUC 14 also forms self-assembled dimers in the solid state, as represented in Fig. 5b.…”

Section: Resultsmentioning

confidence: 99%

Enhancing chalcogen bonding by metal coordination

2022

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Section: Resultsmentioning

confidence: 99%

Enhancing chalcogen bonding by metal coordination

2022

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“…A general synthesis for all monoligated complexes entails mixing 1 equiv of the desired hemilabile ligand 7, 8, 11 , or 12 , prepared via literature methods, 10a,15 with the Pt(II) precursor (Pt(cod)Cl 2 , cod = cyclooctadiene, 1 equiv) in dichloromethane (CH 2 Cl 2 ), resulting in quantitative formation of complexes 9, 10, 13 , and 14 within a few minutes (Scheme 2). 31 P{ 1 H} NMR and, where appropriate, 77 Se{ 1 H} NMR spectroscopies were used to probe the environment of the strong- and weak-binding moieties, respectively.…”

Section: Resultsmentioning

confidence: 99%

Chelating Effect as a Driving Force for the Selective Formation of Heteroligated Pt(II) Complexes with Bidentate Phosphino-Chalcoether Ligands

et al. 2010

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The halide-induced ligand rearrangement reaction (HILR) has been employed to provide selective and exclusive in situ formation of heteroligated Rh(I), Pd(II), and Pt(II) complexes with bidentate phosphino-chalcoether ligands. To gain insights on the nature of this unique reaction, we explored this process via the stepwise addition of bidentate phosphino-chalcoether (P, X; X = S or Se) and relevant monodentate phosphine ligands with a Pt(II) metal precursor. The corresponding monoligated complexes were obtained in quantitative yields by reacting 1 equiv of a P, X bidentate ligand with Pt(II) and were fully characterized via single crystal X-ray diffraction studies and heteronuclear (31P, 77Se, and 195Pt) NMR spectroscopy in solution. These species were further reacted with a second equivalent of either a bidentate ligand or the monodentate ethyl diphenylphosphine ligand, resulting in the clean formation of the heteroligated species or, in the case of the monodentate ligand with an electron-withdrawing bidentate ligand, a mixture of products. On the basis of competitive exchange reactions between these heteroligated, homoligated, and monoligated complexes, we conclude that ligand chelation plays a crucial role in the Pt(II) HILR. The in situ preferable formation of the stable monoligated complex allows for ligand sorting to occur in these systems. In all cases where the heteroligated product results, the driving force to these species is ligand chelation.

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“…As commented above, most hits from the CSD search present an halogen atom as electron donor, basically because chloride is widely used in the synthesis of Pd and Pt complexes. Figure 5a highlights a self-assembled dimer that is formed in the solid state of (1,2-bis(phenylseleno)benzene)-dichlorido-palladium(II) (refcode XILFEE [91]), selected as representative X-ray structure with Se•••Cl contacts. It can be observed that the chloride ligands are located opposite to the C-Se bonds, thus forming four concurrent ChBs and one Pd•••Pd contact.…”

Section: Halogen As Electron Donormentioning

confidence: 99%

Metal Coordination Enhances Chalcogen Bonds: CSD Survey and Theoretical Calculations

Frontera

Bauzá

2022

IJMS

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In this study the ability of metal coordinated Chalcogen (Ch) atoms to undergo Chalcogen bonding (ChB) interactions has been evaluated at the PBE0-D3/def2-TZVP level of theory. An initial CSD (Cambridge Structural Database) inspection revealed the presence of square planar Pd/Pt coordination complexes where divalent Ch atoms (Se/Te) were used as ligands. Interestingly, the coordination to the metal center enhanced the σ-hole donor ability of the Ch atom, which participates in ChBs with neighboring units present in the X-ray crystal structure, therefore dictating the solid state architecture. The X-ray analyses were complemented with a computational study (PBE0-D3/def2-TZVP level of theory), which shed light into the strength and directionality of the ChBs studied herein. Owing to the new possibilities that metal coordination offers to enhance or modulate the σ-hole donor ability of Chs, we believe that the findings presented herein are of remarkable importance for supramolecular chemists as well as for those scientists working in the field of solid state chemistry.

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Versatile routes to selenoether functionalised tertiary phosphines

Cited by 13 publications

References 35 publications

Enhancing chalcogen bonding by metal coordination

Enhancing chalcogen bonding by metal coordination

Chelating Effect as a Driving Force for the Selective Formation of Heteroligated Pt(II) Complexes with Bidentate Phosphino-Chalcoether Ligands

Metal Coordination Enhances Chalcogen Bonds: CSD Survey and Theoretical Calculations

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