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Addition of Organolithium Nucleophiles to the Diiron Allenyl Complex [Fe 2 (CO) 6 (μ-PPh 2 ){μ-η 1 :η 2α,β -(H)C α C β C γ H 2 }]: Synthesis and Characterization of Organodiiron-Coordinated β,γ-Unsaturated Ketones

✍ Scribed by Doherty, Simon; Elsegood, Mark R. J.; Clegg, William; Rees, Nicholas H.; Scanlan, Tom H.; Waugh, Mark

Book ID: 125930712
Publisher: American Chemical Society
Year: 1997
Tongue: English
Weight: 336 KB
Volume: 16
Category: Article
ISSN: 0276-7333
DOI: 10.1021/om970171l

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Nucleophilic Addition of Alcohols to [Fe

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Competitive Nucleophilic Attack at CO an

Competitive Nucleophilic Attack at CO and C β of the Allenyl Group in [Fe 2 (CO) 6 (μ-PPh 2 )(μ-η 1 :η 2 -(H)C α C β C γ H 2 )]. X-ray Crystal Structures of [Fe 2 (CO) 5 (μ-PPh 2 )(μ-η 1 ( O ):η 1 ( C ):η 2 ( C )- {OC(N t BuH)CH 2 }CCH 2 )]·0.5C 6 H 14 and [Fe 2 (CO) 6 (μ-PPh 2 )(μ-η 1 :η 1 -CH 2 C(NCyH)CH 2 ]·MeCN

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Regioselective Addition of tert -BuN⋮C t

Regioselective Addition of tert -BuN⋮C to the α Carbon Atom of the Allenyl Ligand in [Fe 2 (CO) 6 (μ-PPh 2 ){μ-η 1 :η 2α,β -(H)C α C β C γ H 2 }]: Formation of [Fe 2 (CO) 6 (μ-PPh 2 ){μ-η 1 :η 1 -( tert -BuN⋮C)CCCH 3 }] and [Fe 2 (CO) 6 (μ-PPh 2 )(μ-η 1 :η 2 -{ tert -BuNHC(O)CH 2 }CCH 2 )] via Competitive 1,3-Hydrogen Migration and Hydrolysis of the Reactive Allene-Bridged Intermediate [Fe 2 (CO) 6 (μ-PPh 2 ){μ-η 1 :η 1 -( tert -BuNC)HCCCH 2 }]

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Synthesis of “Phosphine Tethered” η 2 -A

Synthesis of “Phosphine Tethered” η 2 -Allene and μ-η 1 :η 2 -Alkenyl Complexes: Facile P−C α Bond Formation and C−H Activation Reactions of Bis(diphenylphosphino)methane with [Fe 2 (CO) 6 (μ-ER){μ-η 1 :η 2α,β -(H)C α C β C γ H 2 }] (E = PPh, R = Ph; E = S, R = t Bu)

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Comparative chemistry of μ-η1 : η2-allen

Comparative chemistry of μ-η1 : η2-allenyl and μ-η1 : η2-acetylide complexes: η5-cyclopentadienyl complexes via alkyne-allenyl coupling in the reactions of PhCCPh with [Ru2(CO 6{μ-η1 : ηβ, γ2-C(Ph)CCH2}(μ-PPh2)] and [Ru2(CO) 6{μ-η1 : η2-CCPh}(μ-PPh2]. X-ray structures of [{Ru2(CO) 4{μ-η2(C,O),η5-C5MePh2(C6H4)(O)}(μ-PPh2)}2] and [Ru2(CO) 5{μ-η2(C,O), η5-C5HPh2(C6H4) (O)}(μ-PPh2)]

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