Reactivity of arenecyclopentadienylruthenium cations

Vol'kenau, N. A.; Bolesova, I. N.; Shul’pina, Lidia S.; Kitaigorodskii, A. N.

doi:10.1016/0022-328x(84)80204-1

Cited by 37 publications

(9 citation statements)

References 8 publications

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“…These results may be compared to those for η 5 -cyclopentadienyl- η 6 -benzene-ruthenium(II) cation; reduction with sodium amalgam under conditions similar to ours has been reported to give varying ratios of η 5 -cyclopentadienyl- η 5 -cyclohexadienylruthenium (presumably resulting from the 19-electron Ru(I) species abstracting H • from a solvent or other molecule, paralleling our observation of RcMe) and ruthenocene (presumably formed by ligand exchange) as the main isolable products. , Products arising from dimerization of the reduced species through the arene, paralleling our observation of RcCH 2 CH 2 Rc, have been observed for other η 5 -cyclopentadienyl- η 6 -areneruthenium(II) derivatives; in these cases the dimerization leads to a μ - η : 5 η 5 -1,1‘-dihydrobiphenyl (or a similar derivative) ligand .…”

Section: Resultssupporting

confidence: 84%

The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts

et al. 2001

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Salts of the ruthenocenylmethylium cation, 1 +, can be synthesized from the reaction of ruthenocenylmethanol with either Brønsted or Lewis acids. The X-ray crystal structures of the tetrakis{3,5-bis(trifluoromethyl)phenyl}borate and trifluoromethanesulfonate salts of 1 + reveal that the methylium carbon is bound to the ruthenium with Ru−C bond lengths in the range 2.251(9)−2.40(1) Å and confirm the description of the cation structure as η 5-cyclopentadienyl-η 6-fulvene-ruthenium(II). The UV−vis spectrum of 1 + shows a d−d transition at an energy similar to those of ruthenocene and the η 5-cyclopentadienyl-η 6-benzeneruthenium(II) cation, but with increased absorptivity. Cyclic voltammetry indicates that 1 + is reduced at considerably less negative potential than its isomer, the η 5-cyclopentadienyl-η 6-benzene-ruthenium(II) cation. Chemical reduction with sodium amalgam in tetrahydrofuran leads to the formation of methylruthenocene, 1,2-bis(ruthenocenyl)ethane, and bis(ruthenocenylmethyl)ether. Reaction of 1 + with triphenylphosphine affords the (ruthenocenylmethyl)triphenylphosphonium cation; the crystal structure of the dichloromethane solvate of its tetrafluoroborate salt has been determined. Density functional calculations closely reproduce the crystallographically determined geometry of 1 + and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity. The calculations suggest that the ferrocenylmethylium cation, 3 +, has a geometry similar to 1 + with similar orbital structure, albeit with considerably more d-character to the occupied frontier orbitals.

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Section: Resultssupporting

confidence: 84%

The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts

et al. 2001

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“…The 1 H NMR spectrum shows two resonances for the methylene hydrogens of the cyclohexadienyl ligands at 2.92 and 2.63 ppm and three resonances for the pentadienyl protons at 5.97, 4.55, and 2.63 ppm, which is the expected number of resonances based on the proposed structure. The chemical shifts also closely match the reported resonances of CpRu(η 5 -C 6 H 7 ) . The cyclopentadienyl ring hydrogens in the 1 H NMR spectrum are a doublet and a triplet, consistent with the proposed symmetrical structure.…”

Section: Resultssupporting

confidence: 82%

Syntheses and Characterization of Ruthenium Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand and Acetonitrile Ligands

et al. 2010

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The reaction of a mixture of isomers of 4,4,8,8-tetramethyl-tetrahydro-s-indacene (1) with Ru 3 -(CO) 12 afforded cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 , (2) in 68% yield. Reaction of 2 with Br 2 gave cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 Br 2 (3) in 88% yield. Reaction of 3 with AgOTf yields cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 4 (μ-Br)][OTf] (4), while reaction of 3 with Me 3 NO and AgOTf yields cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 2 (MeCN) 2 (μ-Br)][OTf] (5). Reaction of 3 under more forcing conditions with AgOTf in MeCN gave cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (CO) 2 (MeCN) 4 ][OTf] 2 (6), while a MeCN/C 6 H 6 solvent combination afforded cis-[{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (η 6 -C 6 H 6 ) 2 ][OTf] 2 (7) in a 64% yield. Removal of the benzene ligands in 7 can be accomplished by first adding Hto the coordinated benzene ligands to afford cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (η 5 -C 6 H 7 ) 2 (10). Subsequent protonation of 10 in MeCN afforded [cis-{(η 5 -C 5 H 3 ) 2 (CMe 2 ) 2 }Ru 2 (MeCN) 6 ][OTf] 2 (8) in 88% yield. Structural data for 4, 5, 7, and 10 are reported.

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“…There has been some interest in preparing sandwich complexes with other carbocyclic aromatic ligands and Tp. The preparation of [Ru(C 6 H 6 )Tp‘] + (Tp‘ = Tp and B(pz) 4 ) and the cyclobutadienyl complexes [Co(Ph 4 C 4 )Tp] + was also the subject of previous reports, and the crystal structure of [Ru(η 6 -C 6 H 6 )(B(pz) 4 ] + was subsequently described. , Several other Tp-containing species with a variety of substituted arenes have been isolated more recently, including [Ru(C 6 H 6 )Tp*] + , , and the reactivity of [Ru(C 6 H 6 )Tp] + (and other substituted-arene analogues) with nucleophiles has also been studied. , Mixed cyclooctatetraene (COT)/Tp‘ (Tp‘ = Tp and Tp*) sandwich complexes of Ti(III) have been reported, and the X-ray crystal structure of the Tp complex has been determined: the Ti center displays η 8 -COT and κ 3 -Tp bonding . A series of trivalent lanthanide Tp‘ sandwich complexes have also been prepared with COT as ancillary ligand, where Tp‘ = Tp and Tp*. − …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Redox Properties of Mixed-Sandwich Complexes of Cyclopentadienyl and Hydrotris(pyrazolyl)borate Ligands with First-Row Transition Metals

2002

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A series of [MCpRTp] n + (CpR = Cp*(pentamethylcyclopentadienyl) or Cp (cyclopentadienyl), Tp = hydrotris(pyrazolyl)borate) complexes have been synthesized by reaction of a suitable MCpR precursor with KTp (CpR = Cp*; n = 0, M = Cr, Fe, Co, Ni; n = 1, M = Cr, Co, Ni; CpR = Cp; n = 0, M = V, Co, Ni; n = 1, M = V, Co). Oxidation with [FeCp2]+ salts or reduction with CoCp2 where appropriate provided easy access to the corresponding M(III) or M(II) species. All of the complexes studied showed reversible M(III)/M(II) redox couples. Similarly [MCpRTpm] n + complexes have also been isolated (Tpm = hydrotris(pyrazolyl)methane; CpR = Cp*, n = 1, M = Fe; CpR = Cp, n = 1 or 2, M = Co). Analytical, NMR, IR, and mass spectroscopic data are consistent with the formulation of these species as mixed-sandwich complexes. Oxidation of VCpTp in MeCN solution yields [VCpTp(MeCN)]+, whereas similar reaction in CH2Cl2 solution yields [VCpTp]+. [VCpTp]+ reacts with σ-donor ligands L, where L = CNtBu and PMe3, to form [VCpTpL]+ species, but is unreactive when L = CO, indicating little π-base character to the V center. Crystal structure determinations were performed for various complexes: CoCp*Tp is unique in displaying κ2-Tp and η5-Cp* coordination, whereas [VCpTp]+, [CoCp*Tp]+, NiCp*Tp, and [CoCpTpm]2+ all display mixed-sandwich structures with κ3-Tp binding. The factors determining the relative conformations of the CpR and Tp ligands are discussed. The structures of [VCpTp(MeCN)]+ and [VCpTp(PMe3)]+ were also determined and show that considerable distortion of the sandwich moiety has occurred to accommodate coordination of the extra ligand. For the MCpRTp complexes a dependence of νB - H on Tp hapticity, ancillary ligand, and oxidation state is observed from IR spectroscopic data in the solid state. IR data obtained in solution suggest that CoCp*Tp is in conformational equilibrium, with a κ3-Tp structure also present. Some of the factors affecting 1H and 13C NMR shifts are discussed and compared with relevant homoleptic analogues. Electrochemical data reveal, in general, that MCp2 and MCp*2 species are more electron rich, although comparisons are best confined to a per metal basis.

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Reactivity of arenecyclopentadienylruthenium cations

Cited by 37 publications

References 8 publications

The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts

The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts

Syntheses and Characterization of Ruthenium Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand and Acetonitrile Ligands

Synthesis, Structures, and Redox Properties of Mixed-Sandwich Complexes of Cyclopentadienyl and Hydrotris(pyrazolyl)borate Ligands with First-Row Transition Metals

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Reactivity of arenecyclopentadienylruthenium cations

Cited by 37 publications

References 8 publications

The Ruthenocenylmethylium Cation: Isolation and Structures of η5-Cyclopentadienyl-η6-fulvene-ruthenium(II) Salts

The Ruthenocenylmethylium Cation: Isolation and Structures of η5-Cyclopentadienyl-η6-fulvene-ruthenium(II) Salts

Syntheses and Characterization of Ruthenium Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand and Acetonitrile Ligands

Synthesis, Structures, and Redox Properties of Mixed-Sandwich Complexes of Cyclopentadienyl and Hydrotris(pyrazolyl)borate Ligands with First-Row Transition Metals

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The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts

The Ruthenocenylmethylium Cation: Isolation and Structures of η⁵-Cyclopentadienyl-η⁶-fulvene-ruthenium(II) Salts