The preparation of mixed ligand ruthenocenes containing bulky cyclopentadienyl ligands. Crystal structures of pentaphenylruthenocene, [Ru(η5-C5Ph5)(η5-C5H5)], pentaparatolylruthenocene, [Ru{η5-C5(p-MeC6H4)5}(η5-C5H5)] and pentaphenylpentamethylruthenocene, [Ru(η5-C5Ph5)(η5-C5Me5)]

Beck, Corina U.; Field, Leslie D.; Hambley, Trevor W.; Humphrey, Paul A.; Masters, Anthony F.; Turner, Peter

doi:10.1016/s0022-328x(98)00622-6

Cited by 13 publications

(6 citation statements)

References 26 publications

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“…However, even prolonged reflux of a solution of [Cp φ *Ru(CO) 2 Br] ( 10 ) and K-pyrrolide would only furnish pyrrolide bound η 1 to ruthenium ( 11 , according to crude NMR), and solvent removal followed by thermolysis of the crude mixture was necessary to get the desired azaruthenocene in 46% yield. This is in good agreement with previously reported syntheses of the nonaza analogues pentaphenylferrocene − and pentaphenylruthenocene 3 …”

Section: Resultssupporting

confidence: 93%

“…On comparing the crystal structures of the nonaza analogues 1,2,3,4,5-pentaphenylferro- and ruthenocene, , we noticed that the mean distance between the metallocene planes increases by ∼0.3 Å on going from Fe to Ru. We speculated that this increase in distance could be enough for the introduction of the sulfoxide auxiliary in the ruthenocene case.…”

Section: Resultsmentioning

confidence: 96%

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Pentamethylated and Pentaphenylated Azaferro- and Azaruthenocenes: Simple and General Methodology for the Preparation of Enantiopure Derivatives

Hansen

Johannsen

2003

J. Org. Chem.

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A methodology for the enantioselective synthesis of planar chiral 2-substituted 1',2',3',4',5'-pentamethylazaferro- and azaruthenocenes is reported. The key step is the introduction of an enantiopure chiral sulfoxide auxiliary via a selective ortho-lithiation with subsequent chromatographic separation of the resulting diastereomers. Cleaving off the sulfoxide auxiliary by treatment with t-BuLi generates an optically pure anion which may be quenched with a variety of electrophiles to give the optically pure azametallocene derivatives. In addition, it was attempted to extend the methodology to encompass 1',2',3',4',5'-pentaphenyl derivatives. It was, however, not possible to attach the chiral sulfoxide auxiliary onto the pentaphenylated azaferrocene, and for the azaruthenocene case, only one diastereomer could be isolated. Most importantly, the sulfoxide group could be cleaved off and the resulting chiral azaruthenocenyl anion was quenched with paraformaldehyde and iodine, resulting in products with ee values of 85% and 99%, respectively.

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Section: Resultssupporting

confidence: 93%

Section: Resultsmentioning

confidence: 96%

Pentamethylated and Pentaphenylated Azaferro- and Azaruthenocenes: Simple and General Methodology for the Preparation of Enantiopure Derivatives

Hansen

Johannsen

2003

J. Org. Chem.

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“…Each step often results in a diminished yield and formation of byproducts that are difficult to remove during workup. Efficient synthetic methods for the preparation of pentasubstituted metallocenes often involve the use of preprepared pentasubstituted Cp ligands, with this strategy resulting in the preparation of a range of pentasubstituted alkyl, − aryl, , and halogenated metallocenes . Pentasubstituted metallocenes incorporating electron-withdrawing substituents such as esters have also been reported, − albeit to a much lesser extent.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Spectroscopic Characterization, and Cytotoxic Evaluation of Pentasubstituted Ruthenocenyl Esters

et al. 2010

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This article details the preparation and spectroscopic characterization of a focused library of new 18-electron ruthenocenyl complexes incorporating pentasubstituted Cp ester [C 5 (CO 2 R) 5 ] -(for R = Me, Et, n-Pr, n-Bu, 2-Pr, 3-Pent, phenyl, and n-thiopropyl), carboxylic acid [C 5 (CO 2 H) 5 ] -, and carboxylate ligands [C 5 (CO 2 H) 4 (CO 2 )] 2-. Each complex has been characterized using Fourier transform IR and NMR spectroscopy and electrospray mass spectrometry, with single-crystal X-ray structural determinations reported for four complexes: [Ru(η 5 -C 5 H 4 (C 5 (CO 2 CH 3 ) 5 )(η 5 -C 5 (CO 2 -CH , -C 5 H 5 )(η 5 -C 5 (CO 2 C 6 H 5 ) 5 )]. Complexes were also evaluated for in vitro cytotoxic activity against a diverse panel of tumorigenic cell lines and a normal human cell line.

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“…Hembre reported the synthesis of Cp*Ru(dppf)Cl/H ( 1f / 2f ) by treating dppf with refluxing Cp*Ru(PPh 3 ) 2 Cl/benzene followed by refluxing NaOMe/MeOH . The first part of this sequence (method C , Scheme ) worked for 1i but not for 1g or 1h ; the latter two complexes were prepared from Cp*Ru(1,5-COD)Cl (method D ) since 1,5-cyclooctadiene is easily displaced from Ru(II). , The Cp*Ru hydrides (except for 2i , see below) were prepared by the usual treatment of the chlorides with refluxing NaOMe/MeOH.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Shaw¹,

Norton²,

Buccella³

et al. 2009

Organometallics

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The bimetallic complexes CpRu(P-P)X [Cp=η 5 -C 5 H 5 ; X=Cl, H; P-P=dppf (1,1 0 -bis(diphenylphosphino)ferrocene), dppr (1,1 0 -bis(diphenylphosphino)ruthenocene), dppo (1,1 0 -bis(diphenylphosphino)-osmocene), dippf (1,1 0 -bis(diisopropylphosphino)ferrocene), dcpf (1,1 0 -bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp*=η 5 -C 5 Me 5 ; X=Cl, H; P-P=dppf, dippf, dppomf (1,1 0 -bis(diphenylphosphino) octamethylferrocene), dppc (1,1 0 -bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X=H, CCPh; P-P=dppc + ), and [Cp*Ru(P-P)L] 2+ (L= CH 3 CN, t-BuCN; P-P= dppc + ) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3 CN][PF 6 ] 2 and [Cp*Ru(dppc)CCPh][PF 6 ] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+ . The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH 3 CN] 2+ . The 1 H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic R-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] + and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give trans-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] + , which forms a dihydrogen complex [Cp*Ru(dppc)(H 2 )] 2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2 )] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.

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The preparation of mixed ligand ruthenocenes containing bulky cyclopentadienyl ligands. Crystal structures of pentaphenylruthenocene, [Ru(η5-C5Ph5)(η5-C5H5)], pentaparatolylruthenocene, [Ru{η5-C5(p-MeC6H4)5}(η5-C5H5)] and pentaphenylpentamethylruthenocene, [Ru(η5-C5Ph5)(η5-C5Me5)]

Cited by 13 publications

References 26 publications

Pentamethylated and Pentaphenylated Azaferro- and Azaruthenocenes: Simple and General Methodology for the Preparation of Enantiopure Derivatives

Pentamethylated and Pentaphenylated Azaferro- and Azaruthenocenes: Simple and General Methodology for the Preparation of Enantiopure Derivatives

Synthesis, Spectroscopic Characterization, and Cytotoxic Evaluation of Pentasubstituted Ruthenocenyl Esters

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

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