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• W2058258510 abstract "Abstract Addition of cyanide ions to the alkynyl(methoxy)carbene complexes [Fe 2 {μ‐CN(Me)(R)}(μ‐CO)(CO){C α (OMe)C β ≡C γ R'}(Cp) 2 ] + (R = Xyl, R' = Tol, 1a ; R = Xyl, R' = Ph, 1b ; R = Xyl, R' = Me 3 Si, 1c ; R = Me, R' = Tol, 1d ; R = Me, R' = Ph, 1e ) occurs selectively at C α to afford the 1,1‐disubstituted σ‐propargyl complexes [Fe 2 {μ‐CN(Me)(R)}(μ‐CO)(CO){C(OMe)(CN)(C≡CR')}(Cp) 2 ] (R = Xyl, R' = Tol, 2a ; R = Xyl, R' = Ph, 2b ; R = Xyl, R' = Me 3 Si, 2c ; R = Me, R' = Tol, 2d ; R = Me,R' = Ph, 2e ). Conversely, the stabilised carbanaions[CH(R) 2 ] – (R = CN, CO 2 Me) add at the C γ position with subsequent hydrogen migration to C β to give the 1‐σ‐buta‐1,3‐dienyl complexes [Fe 2 {μ‐CN(Me)(Xyl)}(μ‐CO)(CO){C α (OMe)=C β HC γ (Tol)=C δ (R) 2 }(Cp) 2 ] (R = CN, 3a ; CO 2 Me, 3b ). No migration is possible in the absence of hydrogen atoms at C δ , therefore addition of [C(Me)(CO 2 Me) 2 ] – to 1a results in the formation of the σ‐allenyl complex [Fe 2 {μ‐CN(Me)(Xyl)}(μ‐CO)(CO){C α (OMe)=C β =C γ (Tol)C δ (Me)(CO 2 Me) 2 }(Cp) 2 ] ( 4 ). Protonation of the neutral complexes 3b and 4 affords the vinyl(methoxy)carbene complexes [Fe 2 {μ‐CN(Me)(Xyl)}(μ‐CO)(CO){C α (OMe)C β H=C γ (Tol)C δ (R)(CO 2 Me) 2 }] + (R = H, 5 ; Me, 6 ), which exist in solution as mixtures of ( E )‐ and ( Z )‐isomers in dynamic equilibrium, as shown by VT NMR studies. The cationic complex 6 shows electrophilic behaviour. Thus, addition of CN – results in the σ‐allyl complex [Fe 2 {μ‐CN(Me)(Xyl)}(μ‐CO)(CO){C α (OMe)(CN)[C β H=C γ (Tol)C δ (Me)(CO 2 Me) 2 ]}(Cp) 2 ] ( 7 ), whereas the reaction with Me 2 NH affords the vinyl acyl complex [Fe 2 {μ‐CN(Me)(Xyl)}(μ‐CO)(CO){C α (O)C β H=C γ (Tol)C δ (Me)(CO 2 Me) 2 }(Cp) 2 ] ( 8 ). The crystal structures of 2b and 3a·CH 2 Cl 2 have been determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)" @default.
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• W2058258510 date "2005-08-01" @default.
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• W2058258510 title "Formation of C–C Bonds in Diiron Complexes by Addition of Carbanions to Alkynyl(methoxy)carbene Ligands" @default.
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• W2058258510 doi "https://doi.org/10.1002/ejic.200500093" @default.
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