Catalytic C–F activation via cationic group IV metallocenes

Lanzinger, Dominik; Höhlein, Ignaz M. D.; Weiß, Sebastian; Rieger, Bernhard

doi:10.1016/j.jorganchem.2014.12.011

Cited by 18 publications

(10 citation statements)

References 47 publications

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“…33 Since this ion was not observed in ethylene (or hexene) polymerization experiments conducted in toluene solution, it was assigned to [Cp 2 Zr(μ-F)(μ-Me)AlMe 2 ] + (8) ostensibly a product of C-F activation, a reaction that is known to be mediated by cationic zirconocene complexes in the presence of TiBAl. 45 The MS-MS spectra of m/z 311 is not entirely consistent with this formulation; it readily loses 16 (CH 4 ) and then 66 Da (C 5 H 6 ) at increased collision energies (Supporting Information Figure S Finally, it was observed that the intensity of this ion was maximal upon initial pumping of solutions of ion-pair 1 and hexene. Prolonged pumping of these solutions led to a pronounced decrease in the intensity of this ion relative to the others present ( Figure 3).…”

Section: Catalyst Speciation At Steady State -Constant Monomer Concenmentioning

confidence: 90%

Catalyst Deactivation Processes during 1-Hexene Polymerization

et al. 2020

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The catalyst [Cp 2 Zr(μ-Me) 2 AlMe 2 ] + [B(C 6 F 5) 4 ] − (1) has been studied by electrospray ionisation mass spectrometry (ESI-MS) in order to better understand the complexities of catalyst deactivation in the polymerisation of 1-hexene. Using offline, online and flow-based methods, we observe that zirconium π-allyl species are unstable in solution and previously unobserved dimethylalane complexes are more stable. The dimethylalane complexes are resistant to further 1-hexene additions and their formation represent a new pathway for catalyst deactivation. File list (2) download file view on ChemRxiv Manuscript20200403.docx (6.24 MiB) download file view on ChemRxiv SupportingInformation20200403.docx (1.38 MiB)

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Section: Catalyst Speciation At Steady State -Constant Monomer Concenmentioning

confidence: 90%

Catalyst Deactivation Processes during 1-Hexene Polymerization

et al. 2020

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Section: Catalyst Speciation At Steady State -Constant Monomer Concentrationmentioning

confidence: 90%

Catalyst Deactivation Processes During 1-Hexene Polymerization

Joshi¹,

Zijlstra²,

Collins³

et al. 2020

Preprint

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The catalyst [Cp2Zr(μ-Me)2AlMe2]+[B(C6F5)4]− (1) has been studied by electrospray ionisation mass spectrometry (ESI-MS) in order to better understand the complexities of catalyst deactivation in the polymerisation of 1-hexene. Using offline, online and flow-based methods, we observe that zirconium π-allyl species are unstable in solution and previously unobserved dimethylalane complexes are more stable. The dimethylalane complexes are resistant to further 1-hexene additions and their formation represent a new pathway for catalyst deactivation.

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“…However, the catalytic conversion of 3,3,3-trifluoropropene into CF 2 =CHCH 3 has been demonstrated by Holland and co-workers using an iron fluorido complex in the presence of silanes. 27c Note also that 3,3,3-trifluoropropene C(sp 3 )-F bond activation reactions followed by C-C coupling reactions with aromatics or alkynes with Zr 49 or Ni 50 catalysts have been described. A unique example consists of the dehydrogenative silylation and hydrosilylation of 3,3,3-trifluoropropene with Ru, Rd or Pd catalysts described in the early 80s by Ojima et al 51…”

Section: Account Synlettmentioning

confidence: 99%

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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Catalytic C–F activation via cationic group IV metallocenes

Cited by 18 publications

References 47 publications

Catalyst Deactivation Processes during 1-Hexene Polymerization

Catalyst Deactivation Processes during 1-Hexene Polymerization

Catalyst Deactivation Processes During 1-Hexene Polymerization

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

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