Ligand substitution in the tetrahedrane clusters RCCo2Mo(η5-indenyl)(CO)8 with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): Influence of the carbyne and indenyl ligands on the stability of the substitution products and X-ray diffraction structures of HCCo2Mo(η5-indenyl)(CO)6(μ-bpcd) and CoMo(η5-indenyl)(μ-CPh)(CO)2(μ-bpcd)Cl

Watson, William H.; Poola, Bhaskar; Richmond, Michael G.

doi:10.1016/j.jorganchem.2006.08.095

Cited by 4 publications

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“…Byers and Brown have suggested a radical mechanism for the formation of this complex, either from Re 2 (CO) 9 H and Re(CO) 5 radicals or from Re 2 (CO) 9 and Re(CO) 5 H. In addition, a light yellow fraction obtained during the column chromatographic separation of the rhenium titanoxycarbene reaction mixture was identified as [Re(CO) 5 Cl]. Evidence of chlorine abstraction from dichloromethane in a radical mechanism by a tetrahedrane cluster [RCCo 2 Mo(η 5 -indenyl)(CO) 8 ] (R = H; Ph), after breaking of the Mo−Co and Co−Co bonds, has recently been published by Watson et al Also, reaction of a ruthenium carbonyl complex [Ru 2 (CO) 2 (π-CO)H(π-CCPh)(π-dppm) 2 ] with a chlorinated solvent, CH 2 Cl 2 , resulted in ligand substitution by a solvent chlorine atom to give [Ru 2 (CO) 2 (π-CO)Cl(π-CCPh)(π-dppm) 2 ] . Alternatively, labile chloride ions lost from the titanocene dichloride metalating agent could offer another source of the chlorine atom.…”

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confidence: 99%

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

et al. 2011

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Fischer carbene complexes of the group VII transition metals (Mn and Re) containing at least two or three different transition metal substituents, all in electronic contact with the carbene carbon atom, were synthesized. The structural features and their relevance to bonding in the carbene multimetal compounds were investigated, as they represent indicators of possible reactivity sites in polymetallic carbene assemblies. For complexes of the type [ML(x){C(OR)R'}] (ML(x) = MnCp(CO)(2) or Re(2)(CO)(9)), ferrocenyl (Fc) was chosen as the R' substituent, while the OR substituent was systematically varied between an ethoxy or a titanoxy group, to yield the complexes 1a (ML(x) = MnCp(CO)(2), R = Et, R' = Fc), 2a (ML(x) = MnCp(CO)(2), R = TiCp(2)Cl, R' = Fc), 3a (ML(x) = Re(2)(CO)(9), R = Et, R' = Fc), and 4a (ML(x) = Re(2)(CO)(9), R = TiCp(2)Cl, R' = Fc). Direct lithiation of the ferrocene with n-BuLi/TMEDA at elevated temperatures, followed by the Fischer method of carbene preparation, resulted in formation of the novel biscarbene complexes with bridging ferrocen-1,1'-diyl (Fc') substituents [{π-Fe(C(5)H(4))(2)-C,C'}{C(OEt)ML(x)}(2)] (1b, ML(x) = MnCp(CO)(2); 3b, ML(x) = Re(2)(CO)(9)) or the unusual bimetallacyclic bridged biscarbene complexes [{π-TiCp(2)O(2)-O,O'}{π-Fe(C(5)H(4))(2)-C,C'}{CML(x)}(2)] (2b, ML(x) = MnCp(CO)(2); 4b, ML(x) = Re(2)(CO)(9)). The target compounds that were isolated displayed a variety of different geometric isomers and conformations. The greater reactivity of the binary dirhenium acylates in solution, compared to that of the cyclopentadienyl manganese acylate, resulted in a complex reaction mixture. Although the stabilization of hydroxycarbene or hydrido-acyl intermediates of dirhenium carbonyls could not be achieved, their existence in solution was confirmed by the isolation of [(π-H)(2)-(Re(CO)(4){C(O)Fc})(2)] (8), the unique dichloro-bridged biscarbene complex fac-[(π-Cl)(2)-(Re(CO)(3){C(OEt)Fc})(2)] (6), the known hydrido complex [Re(3)(CO)(14)H] (5), the acyl complex [Re(CO)(5){C(O)Fc}] (7), and the aldehyde-functionalized eq-[Re(2)(CO)(9){C(OTiCp(2)Cl)(Fc'CHO)}] (9).

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Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

et al. 2011

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2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters

Lin

Нестеров

Richmond

2013

Journal of Organometallic Chemistry

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Heterometallic Derivatives of the Unsaturated Methyl-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CH₃)(μ-PCy₂)(CO)₂]. Photochemical Generation of Methylidyne-Bridged Clusters

et al. 2010

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The photochemical reactions of the methyl-bridged complex [Mo 2 Cp 2 (μ-CH 3 )(μ-PCy 2 )(CO) 2 ] ( 1) (Cp = η 5 -C 5 H 5 ) with the carbonyl complexes [M(CO) 6 ] (M = Cr, Mo, W) and [MnCp 0 (CO) 3 ] (Cp 0 = η 5 -C 5 H 4 CH 3 ) give the corresponding electron-precise methylidyne-bridged derivatives [MMo 2 Cp 2 (μ 3 -CH)(μ-PCy 2 )(CO) 7 ] (Mo-Mo = 2.9340(13) A ˚for M = W) and [MnMo 2 Cp 2 Cp 0 (μ 3 -CH)(μ-PCy 2 )(CO) 4 ] (Mo-Mo = 2.9678(6) A ˚) in good yields. Under similar conditions, the reaction of 1 with [Ru 3 (CO) 12 ] gives the 46-electron methylidyne-bridged cluster [Mo 2 RuCp 2 (μ 3 -CH)(μ-PCy 2 )(CO) 5 ] (Mo-Mo = 2.6824(7) A ˚), along with a small amount of the methoxy-bridged analogue [Mo 2 RuCp 2 (μ 3 -OCH 3 )(μ-PCy 2 )(CO) 5 ]. A related iron species [FeMo 2 Cp 2 (μ 3 -OCH 3 )(μ-PCy 2 )(CO) 5 ] (Mo-Mo = 2.667(1) A ˚) can be prepared in moderate yield from the reaction of the 30-electron methyl complex [Mo 2 Cp 2 (μ-κ 1 :η 2 -CH 3 )(μ-PCy 2 )(μ-CO)] and [Fe 2 (CO) 9 ]. Compound 1 reacts with [Fe 2 (CO) 9 ] at room temperature to give the acetyl-bridged cluster [FeMo 2 Cp 2 {μ 3 -κ 1 :η 2 :κ 1 -C(O)CH 3 }(μ-PCy 2 )(CO) 5 ] (Mo-Mo = 2.8474(5) A ˚) in high yield, which undergoes full cleavage of the acetyl C-O bond under thermal or photolytic activation to give the oxoethylidyne derivative [FeMo 2 Cp 2 (μ 3 -CCH 3 )(μ-PCy 2 )(O)(CO) 4 ] (Mo-Mo = 2.8469(4) A ˚). Under photochemical conditions, however, compound 1 reacts with [Fe 2 (CO) 9 ] to give the methylidyne-bridged compound [Fe 2 Mo 2 Cp 2 (μ 4 -CH)(μ-PCy 2 )(CO) 8 ] (Mo-Mo = 2.8351(7) A ˚) as major species. This 60-electron cluster displays a butterfly Mo 2 Fe 2 core with no agostic interactions of the methylidyne ligand.Article

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Cited by 4 publications

References 50 publications

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters

Heterometallic Derivatives of the Unsaturated Methyl-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CH₃)(μ-PCy₂)(CO)₂]. Photochemical Generation of Methylidyne-Bridged Clusters

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Cited by 4 publications

References 50 publications

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

Synthesis, Characterization, and Structural Studies of Multimetallic Ferrocenyl Carbene Complexes of Group VII Transition Metals

2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters

Heterometallic Derivatives of the Unsaturated Methyl-Bridged Complex [Mo2(η5-C5H5)2(μ-CH3)(μ-PCy2)(CO)2]. Photochemical Generation of Methylidyne-Bridged Clusters

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Heterometallic Derivatives of the Unsaturated Methyl-Bridged Complex [Mo₂(η⁵-C₅H₅)₂(μ-CH₃)(μ-PCy₂)(CO)₂]. Photochemical Generation of Methylidyne-Bridged Clusters