Notizen: Oxydative Additionsreaktionen von „Titanocen“

Köpf, Hartmut; Block, B.

doi:10.1515/znb-1968-1122

Cited by 18 publications

(3 citation statements)

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“…The ligating behavior of organosulfur compounds to multimetallic sites and subsequent transformations are important in different aspects. Organic sulfides such as RSH and RSSR are the usual source of the thiolate SR ligands through activation of the S−H and S−S bonds, respectively, in the synthesis of thiolato complexes containing M−SR bonds. , In addition, the M−SR unit can transfer the thiolate ligand to other metal centers, and thus, M−SR can act as a thiolate ligand source in the synthesis of thiolato complexes …”

Section: Introductionmentioning

confidence: 99%

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

et al. 2005

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Reactions of (1) with alkyl disulfides RSSR (R = Me, Et, Pr, Bun) in refluxing dichloromethane yielded the series of new mixed-metal and mixed-ligand bridged compounds (R = Me (4a), Et (4b), Pr (4c), Bun (4d)), (R = Me (5a), Et (5b), Pr (5c), Bun (5d)), and (R = Me (6a), Et (6b), Pr (6c), Bun (6d)). All except 6c were characterized by single-crystal X-ray diffraction analysis. Formation of compounds 4−6 indicates a general procedure for cleavage of the S−S bonds of alkyl disulfides under mild conditions. Molecular structures of compounds 6a,b,d reveal the first transformation of the bridging PPh2 ligand of 1 to give the hybrid ligands Ph2PSR (R = Me, Et, Bun) via P−S bond formation. The average Mo−W bond distance (2.8255 Å) in the 34e dimers (4a−d, 6a,b,d) is shorter than that in the 32e dimers (5a−d), 2.8494 Å. This appears quite unusual, according to the 18e rule. DFT calculations have been performed to investigate this unusual observation. Characterization of the substitution products (7) and (8; COD = cyclooctadiene) leads to the conclusion that carbonyl ligands on the Mo sites are more labile than those on the W sites.

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Section: Introductionmentioning

confidence: 99%

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

et al. 2005

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“…Alternatively, thiolate complexes may be generated by oxidative addition of alkyl and aryl disulfides to transition-metal complexes. The result may be either mononuclear bis(thiolate) ( I ) or dinuclear complexes with bridging thiolate ligands of types IIa and IIb according to Scheme 1 …”

Section: Introductionmentioning

confidence: 99%

Facile S−S Bond Activation of Alkyl and Aryl Disulfides by [RuCp(CH₃CN)₃]⁺: Formation of Dinuclear Ru(III)−Ru(III) Complexes with Bridging Thiolate Ligands

et al. 2004

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We describe a way to enter into dinuclear RuCp thiolate chemistry, since hitherto only the RuCp* derivatives have been available. When the labile cationic complex [RuCp(CH 3 -CN) 3 ] + is reacted with alkyl or aryl disulfides RSSR (and likewise PhSeSePh), oxidative addition takes place. As a result, dinuclear Ru(III)-Ru(III) complexes of the type [CpRu-(CH 3 CN)(µ-SR) 2 (CH 3 CN)RuCp](PF 6 ) 2 are formed, featuring a metal-metal single bond and bridging thiolate ligands. The reaction of [RuCp(CH 3 CN) 3 ] + with bis(2-pyridyl) disulfide affords, depending on the reaction conditions, either the dinuclear complex [CpRu(µ-pyS) 2 RuCp](PF 6 ) 2 or the mononuclear complex [CpRu(κ 2 N,S-pyS) 2 ]PF 6 . The substitutionally labile acetonitrile ligands in [CpRu(CH 3 CN)(µ-SR) 2 (CH 3 CN)RuCp](PF 6 ) 2 are readily replaced by other donor ligands. For instance, treatment of [CpRu(CH 3 CN)(µ-S-t-Bu) 2 (CH 3 CN)RuCp]-(PF 6 ) 2 with KBr affords the neutral complex CpRuBr(µ-S-t-Bu) 2 BrRuCp, while with t-BuSH the dinuclear complex sym-[CpRu(µ-S-t-Bu) 3 RuCp]PF 6 containing three bridging thiolate ligands is formed. Representative X-ray structures are presented.

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“…In the present contribution we are concerned with thiolate complexes made available through oxidative addition of alkyl or aryl disulfides to transition-metal complexes in low oxidation states. In this way either mononuclear bis-thiolate ( I ) or dinuclear complexes with bridging thiolate ligands of types IIa and IIb are generated according to Scheme . In a recent paper 5 we have investigated the potential of the labile complex [RuCp(CH 3 CN) 3 ] + in this respect.…”

Section: Introductionmentioning

confidence: 99%

Reaction of Diaryl Disulfides with RuTp(COD)Cl in N,N‘-Dimethylformamide: Formation of 2-(Arylmercapto)aryl Mercaptan Complexes

et al. 2004

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H 4 R)-(CO)] containing 2-arylmercapto-arylmercaptan and CO ligands. The formation of this unusual product involves decomposition of the solvent DMF with release of the base HNMe 2 acting as HCl scavenger. This outcome contrasts sharply with an otherwise similar reaction of disulfides with cationic [RuCp(CH 3 CN) 3 ] + , investigated previously, generating dinuclear Ru(III)-Ru(III) complexes with bridging thiolate ligands.

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Notizen: Oxydative Additionsreaktionen von „Titanocen“

Cited by 18 publications

References 0 publications

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

Facile S−S Bond Activation of Alkyl and Aryl Disulfides by [RuCp(CH₃CN)₃]⁺: Formation of Dinuclear Ru(III)−Ru(III) Complexes with Bridging Thiolate Ligands

Reaction of Diaryl Disulfides with RuTp(COD)Cl in N,N‘-Dimethylformamide: Formation of 2-(Arylmercapto)aryl Mercaptan Complexes

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Notizen: Oxydative Additionsreaktionen von „Titanocen“

Cited by 18 publications

References 0 publications

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Bun) by Heterodinuclear Phosphido-Bridged CpW(CO)2(μ-PPh2)Mo(CO)5

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Bun) by Heterodinuclear Phosphido-Bridged CpW(CO)2(μ-PPh2)Mo(CO)5

Facile S−S Bond Activation of Alkyl and Aryl Disulfides by [RuCp(CH3CN)3]+: Formation of Dinuclear Ru(III)−Ru(III) Complexes with Bridging Thiolate Ligands

Reaction of Diaryl Disulfides with RuTp(COD)Cl in N,N‘-Dimethylformamide: Formation of 2-(Arylmercapto)aryl Mercaptan Complexes

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Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

Activation of the S−S Bonds of Alkyl Disulfides RSSR (R = Me, Et, Pr, Buⁿ) by Heterodinuclear Phosphido-Bridged CpW(CO)₂(μ-PPh₂)Mo(CO)₅

Facile S−S Bond Activation of Alkyl and Aryl Disulfides by [RuCp(CH₃CN)₃]⁺: Formation of Dinuclear Ru(III)−Ru(III) Complexes with Bridging Thiolate Ligands