The hydrogenation reaction of [Ru3(CO)10(C6F5)2P(CH2)2P(C6F5)2]: Migration of a C6F5 group from a phosphorus to a ruthenium atom. X-ray crystal structures of [Ru3(CO)9(μ-H){μ2-(C6F5)PCH2CH2P(C6F5)2}], [Ru3(CO)7(μ-H)3(η1-C6F5){μ3-PCH2CH2P(C6F5)2}] and [Ru3(CO)8(μ-H)2{μ3-PCH2CH2P(C6F5)2}]

Sánchez-Cabrera, Gloria; Leyva, Marco A.; Zuno–Cruz, Francisco J.; Hernández-Cruz, María G.; Rosales-Hoz, Marı́a J.

doi:10.1016/j.jorganchem.2009.01.033

Cited by 7 publications

(2 citation statements)

References 27 publications

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“…The complex series of C–F and P–C bond cleavage steps, together with P–F and C–H bond formation, − necessary to generate Ru-PF 2 (C 6 F 5 ) and Ru-C 6 F 5 groups and C 6 F 5 H, in tandem with the lack of any observable intermediates, make it impossible to propose a credible mechanism to account for the formation of 2 . We therefore decided to adopt an alternative approach, to see if PCF displayed related activation chemistry with different ruthenium hydride precursors.…”

Section: Resultsmentioning

confidence: 99%

C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF

et al. 2018

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The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is the five-coordinate complex Ru(IMe4)2(PF2{C6F5})(C6F5)H (2), which is formed via a complex series of C–F/P–C bond cleavage and P–F bond formation steps. In contrast, hydrodefluorination of all six ortho C–F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF (3). NaBArF 4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF 4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. The treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv) afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3, respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).

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Section: Resultsmentioning

confidence: 99%

C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF

et al. 2018

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“…147 Furthermore, pentafluorophenyl migration from a bis(pentafluorophenyl)phosphine group to a metal centre has been reported to occur on rhodium carbonyl clusters containing P(C 6 F 5 ) 2 groups. 148 Mass spectrometry data for the POCCP compounds reported herein also indicated that the P−C bond of the bis(pentafluorophenyl)phosphinite group was prone to cleavage. Data obtained for the POCCP methyl complex 45 subsequently synthesised (vide infra) revealed large peaks corresponding to [M−C 6 F 5 +MeOH] + (690 amu) and [M−C 6 F 5 +NCMe] + (699 amu), as well as the expected peaks due to loss of a methyl group.…”

Section: Methylation Of Pincer Chloride Complexesmentioning

confidence: 55%

Late Transition Metal Complexes of Pentafluorophenylphosphino-Pincer Ligands

Anderson¹

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<p>This thesis details the synthesis of new examples of electron-poor pincer ligands, featuring bis(pentafluorophenyl)phosphine donors attached to 1,3-substituted phenylene or 2,6-substituted pyridine backbones, to create tridentate PCP and PNP ligands. The effect of the ligands’ electronic nature on the coordination chemistry and ease of pincer complex synthesis with late transition metals is discussed, as is the catalytic activity of the resultant palladium pincer complexes in the Heck and Suzuki reactions. Symmetric PCP and PNP ligands possessing bis(pentafluorophenyl)phosphinite and bis(pentafluorophenyl)phosphoramine functionalities were synthesised by reaction of bis(pentafluorophenyl)phosphine bromide with resorcinol, 3-hydroxybenzyl-di- tert -butylphosphine, 2,6-diaminopyridine, or 2,6-dihydroxypyridine, affording 1,3- [(C6F5)2PO]2C6H4 (POCOPH, 1), 1-[(C6F5)2PO]-3-(tBu2PCH2)2C6H4 (POCCPH, 3), 2,6-[(C6F5)2PNH]2C6H3N (PNNNP, 10), and 2,6-[(C6F5)2PO]2C6H3N (PONOP, 11) respectively. The previously reported 1,3-[(C6F5)2PCH2]2C6H4 (PCCCPH, 2) was also synthesised, with the literature yield improved upon by the use of magnesium-anthracene to generate the required Grignard reagent. The coordination chemistry of the POCOPH ligand 1 with platinum(0) alkene and platinum(II) dimethyl precursors revealed an affinity for the formation of cis-bridged oligomeric structures. The dimer [(POCOPH)Pt(nb)]2 (14, nb = norbornene) was isolated and crystallographically characterised from the reaction between 1 and [Pt(nb)3]. The solid state structure revealed the presence of stabilising - interactions between the aromatic ligand backbones, which were also observed in solution by 1H NMR spectroscopy. Reactions of ligand 1 with platinum and palladium dichloride or chloromethyl starting materials led to rare examples of cis,trans-dimers of the type cis,trans-[(POCOPH)MClX]2 (M = Pd, Pt; X = Cl, Me). In part due to facile dimer formation with 1, metallation of the ligand backbone to form the tridentate pincer complex [(POCOP)PtCl] (25) required long reaction times and high temperatures. It was observed that platinum dichloride starting materials with more strongly binding ancillary ligands were less prone to oligomer formation, and could facilitate more rapid metallation to from 25. More facile pincer complex formation was also observed for more electron-rich ligands with both PCP and PNP pincer ligands. The electron poor platinum and palladium POCOP, PCCCP, and POCCP pincer complexes (where the free ligand had been deprotonated upon metallation) were synthesised and subsequently converted into the metal carbonyl species [(PCP)M(CO)]+. Analysis of C−O stretching frequencies by infrared spectroscopy confirmed complexes of POCOP ligand 1 were the most electron poor, while those of POCCP ligand 3 were the most electron rich. Decarbonylation of the palladium pincer complexes was observed in solution and in the solid state, and was more facile for complexes with a higher wavenumber C−O stretch. Reaction of the [(PCP)PtCl] pincer complexes with methyl nucleophiles revealed that treatment with methylmagnesium iodide resulted in halide exchange, while methyllithium promoted nucleophilic attack at phosphorus. Spectroscopic data indicated that in one instance this led to pentafluorophenyl migration to the metal centre to form a [(PCP)Pt(C6F5)] complex. Dimethylzinc was successful in methylating the platinum PCP complexes; however, it was observed to degrade the palladium PCP pincer complexes. Treatment of the rhodium PNP pincer complex [(PNNNP)RhCl] (49) with dimethylzinc also resulted in degradation, which spectroscopic evidence indicated proceeded via ligand deprotonation and the formation of a zinc adduct of 49. Low temperature protonolysis of the [(PCP)PtMe] species did not reveal any information about possible interactions between the metal and liberated methane. The catalytic activity of the electron-poor [(PCP)PdCl] complexes were assessed in the Heck and Suzuki cross-coupling reactions. The complexes of 1, 2, and 3 were all found to possess only modest activity in the Heck reaction, functioning as precatalysts which decomposed to give catalytically-active Pd(0) colloids. Under milder Suzuki reaction conditions, the most electron-poor complex, [(POCOP)PdCl] (28) proved to be one of the most active pincer catalysts known for this reaction, able to achieve a turnover number of 176,000 for the coupling of electronically-deactivated aryl bromides and phenylboronic acid. Mercury poisoning tests revealed that Suzuki reactions catalysed by 28 proceeded via a homogeneous active species.</p>

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Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

Hernández-Cruz

Zuno–Cruz

Alvarado‐Rodríguez

et al. 2016

Journal of Organometallic Chemistry

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The hydrogenation reaction of [Ru3(CO)10(C6F5)2P(CH2)2P(C6F5)2]: Migration of a C6F5 group from a phosphorus to a ruthenium atom. X-ray crystal structures of [Ru3(CO)9(μ-H){μ2-(C6F5)PCH2CH2P(C6F5)2}], [Ru3(CO)7(μ-H)3(η1-C6F5){μ3-PCH2CH2P(C6F5)2}] and [Ru3(CO)8(μ-H)2{μ3-PCH2CH2P(C6F5)2}]

Cited by 7 publications

References 27 publications

C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF

C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF

Late Transition Metal Complexes of Pentafluorophenylphosphino-Pincer Ligands

Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

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The hydrogenation reaction of [Ru3(CO)10(C6F5)2P(CH2)2P(C6F5)2]: Migration of a C6F5 group from a phosphorus to a ruthenium atom. X-ray crystal structures of [Ru3(CO)9(μ-H){μ2-(C6F5)PCH2CH2P(C6F5)2}], [Ru3(CO)7(μ-H)3(η1-C6F5){μ3-PCH2CH2P(C6F5)2}] and [Ru3(CO)8(μ-H)2{μ3-PCH2CH2P(C6F5)2}]

Cited by 7 publications

References 27 publications

C–F Bond Activation of P(C6F5)3by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF

C–F Bond Activation of P(C6F5)3by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF

Late Transition Metal Complexes of Pentafluorophenylphosphino-Pincer Ligands

Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters

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C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF

C–F Bond Activation of P(C₆F₅)₃by Ruthenium Dihydride Complexes: Isolation and Reactivity of the “Missing” Ru(PPh₃)₃H(halide) Complex, Ru(PPh₃)₃HF