A Structurally Characterized Fluoroalkyne

Hall, Lewis M.; Tew, David P.; Pridmore, Natalie E.; Whitwood, Adrian C.; Lynam, Jason M.; Slattery, John M.

doi:10.1002/anie.201702401

Cited by 16 publications

(15 citation statements)

References 29 publications

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“…These characteristics were also found with 5b , as shown in Figure S8. Interestingly, a dichromatic nature has been reported for the related fluorovinylidene complex [Cp*Ru(CCHF)(dppe)][PF 6 ], which was isolated as green crystals without solvation and orange crystals with CH 2 Cl 2 solvate, although the reason was not clarified. , …”

Section: Results and Discussionmentioning

confidence: 99%

“…Interestingly, a dichromatic nature has been reported for the related fluorovinylidene complex [Cp*Ru(CCHF)(dppe)][PF 6 ], which was isolated as green crystals without solvation and orange crystals with CH 2 Cl 2 solvate, although the reason was not clarified. 20,21 The origin of the dichromatic phenomena for 2a, 3a,b, and 5b was clarified by carefully analyzing their crystal structures, and the important structural parameters are summarized in Table 2. We found that intramolecular CH•••O hydrogen bonds between one of the methylene CH bonds in the dppe ligand and the EO (E = P, S) moieties were formed only in the red crystals of 2a and 5b and red-purple crystals of 3a,b.…”

Section: ■ Introductionmentioning

confidence: 99%

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Ruthenium Vinylidene Complexes Generated by Selective 1,2-Migration of P- and S-Substituents: Synthesis, Structures, and Dichromism Arising from an Intramolecular CH···O Hydrogen Bond

et al. 2020

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Investigation of the vinylidene rearrangement of phosphorus-and sulfur-substituted internal alkynes at a ruthenium center unveiled selective 1,2-migration of P-and S-substituents and unexpected dichromatic behaviors of a part of the resulting vinylidene complexes. Reactions of [CpRu(dppe)Cl] and R 1 C CR 2 , where R 1 = alkyl, Ar and R 2 = P(O)(OR) 2 , P(O)R 2 , SR, SO 2 R, in the presence of NaBAr F 4 afforded the corresponding vinylidene complexes [CpRu{CC(R 1 )(R 2 )}(dppe)][BAr F 4 ], which were fully characterized by NMR and elemental analysis and, in some cases, X-ray diffraction analysis. 13 C-labeling experiments disclosed selective migration of the P-and Ssubstituents. To our surprise, some of the products displayed dichromatic characters: although solutions of all the vinylidene products are yellow, several products were obtained as yellow and red crystals, others as red-purple crystals, and the rest as yellow crystals. UV−vis absorption spectra for the complexes displaying a dichromatic nature were recorded both in solution and in the solid state. X-ray diffraction analysis revealed that an intramolecular CH•••O hydrogen bond between one of the methylene CH bonds in the dppe ligand and the EO group (E = P, S) is present in the red and the red-purple crystals, which affects the conformation of the vinylidene ligand. In contrast, such hydrogen bonds were not observed in the yellow crystals. Time-dependent density functional theory (TD-DFT) analysis based on the crystal structures revealed that the structural changes of the vinylidene ligand upon the hydrogen bonding account for the dichromism.

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Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Ruthenium Vinylidene Complexes Generated by Selective 1,2-Migration of P- and S-Substituents: Synthesis, Structures, and Dichromism Arising from an Intramolecular CH···O Hydrogen Bond

et al. 2020

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“…Although C-F bonds are stronger than C-H bonds, there is hitherto no clear correlation with any selectivity. 62 On a first glance, these reactivity pattern resemble those widely studied for fluoroaromatics. However, olefins allow for different reaction steps such as insertion or -Fand -H-elimination reactions.…”

Section: Account Synlettmentioning

confidence: 57%

Rhodium(I) Complexes as Useful Tools for the Activation of Fluoroolefins

Talavera

Braun²

2020

Synlett

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In this account we describe studies on the reactivity of rhodium(I) complexes of the type [Rh(E)(PEt3)3], where E represents hydrido, fluorido, germyl, boryl or silyl ligands, towards fluorinated olefins. The results are compared with those reported by other research groups on fluoroolefins, as well as with the chemistry of compounds [Rh(E)(PEt3)3] towards fluoroaromatics in terms of selectivity and mechanisms.1 Introduction2 Reactivity Towards Fluoroolefins2.1 Reactivity of Hexafluoropropene2.2 Reactivity of (E)-1,2,3,3,3-Pentafluoropropene2.3 Reactivity of 2,3,3,3-Tetrafluoropropene and (E)-1,3,3,3-Tetrafluoropropene2.4 Reactivity of 3,3,3-Trifluoropropene2.5 Reactivity of Pentafluorostyrene3 Conclusion and Perspective

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“…Indeed, there is literature precedence for the generation of alkynyl complexes from vinylidene complexes in presence of a base. [55][56][57][58] Thus, a vacant coordination site can allow for a 1,2-uorine shi to yield a putative vinylidene complex [Rh(F)(]C]CHCF 3 )(PEt 3 ) 2 ] bearing a rhodium-bonded uorido ligand (Scheme 2). The latter complex would eliminate HF followed by an association of PEt 3 and form [Rh(C^CCF 3 )(PEt 3 ) 3 ] (6).…”

Section: Resultsmentioning

confidence: 99%