Convenient routes to mono- and dinuclear (C5Me5)iron(II) complexes bearing acyl, alkynyl, aryl and thienyl ligands

Kiesewetter, Jens; Poignant, Geraldine; Guerchais, Véronique

doi:10.1016/s0022-328x(99)00578-1

Cited by 9 publications

(2 citation statements)

References 18 publications

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“…The IR spectrum in C 6 D 6 showed two intense absorption bands at 2024 and 1979 cm −1 attributed to νCO and another absorption band at 2106 cm −1 attributed to νC=C. These bands are comparable to those reported for Cp*(OC) 2 Fe(C≡C−R) complexes (R=H, Ph, 9,9‐dibutyl‐2‐fluorenyl, and SiMe 3 , 2005–2019 and 1966–1968 cm −1 , and 2036–2095 cm −1 , respectively) [13,18b,19] …”

Section: Resultssupporting

confidence: 74%

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

et al. 2022

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The selective fragmentation of internal alkynyl esters RC≡CCO2Me into RC≡C, C=O, and OMe fragments was investigated using a gallane(pyridyl)iron complex Cp*(OC)Fe{(η1‐HGaMes2)(η1‐2‐C5H4N)} (1, Cp*: η5‐C5Me5, Mes: 2,4,6‐Me3C6H2). The reaction of complex 1 with RC≡CCO2Me (R=Ph, CO2Me) in C7D8 (toluene) at 100 °C for 0.5 h proceeded via selective C−O and C−C bond cleavage to afford η1‐alkynyliron complex Cp*(OC)2Fe(C≡CR) (R=Ph (5 a), CO2Me (5 b)) and 4‐membered Ga2O2 cyclic gallane [Mes2GaOMe]2 (3). In contrast, the reaction of 1 with methyl propiolate HC≡CCO2Me yielded a complex mixture, including gallane 3, Cp*(OC)2Fe(C≡CH) (5 c), and Cp*(OC)Fe(C≡CCO2Me)(GaMes2)(H) (F). The oxidative addition of the terminal H−C bond to the iron center occurred via the reaction of complex 1 with trimethylsilylacetylene (TMSA) and the photochemical reaction of dimesitylgallyliron complex Cp*(OC)2FeGaMes2 (4) with TMSA to afford η1‐alkynyl(gallyl)(hydride)iron complex Cp*(OC)Fe(C≡CSiMe3)(GaMes2)(H) (6).

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Section: Resultssupporting

confidence: 74%

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

et al. 2022

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“…The spectra of 7a + in CH 3 CN ( ϵ = 37.5) and CH 2 Cl 2 ( ϵ = 10.7) are almost identical, that is no variation of the band energy and shape was observed. Moreover, there is no dependence of the band energy and shape on ionic strength up to an electrolyte concentration of 0.2 M in [ n Bu 4 N][BF 4 ] 6i,7h,10. The analysis of the bands gives a bandwidth for the lower energy band I (Figure 4), Δ$\tilde {\nu}$ 1/2 = 1000 cm –1 , which is much below the theoretical value (3630 cm –1 ) predicted by the Hush equation for a localised mixed‐valence (class II) symmetric system,14Δ$\tilde {\nu}$ 1/2 = (2310$\tilde {\nu}$ c ) 1/2 cm –1 , where $\tilde {\nu}$ c is the frequency of the maximum.…”

Section: Resultsmentioning

confidence: 99%

A Joint Experimental and Computational Study on the Electronic Communication in Diethynylaryl‐Bridged (η⁵‐C₅H₅)Fe(η²‐dppe) and (η⁵‐C₅H₅)Fe(CO)₂ Units

et al. 2006

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A family of bimetallic complexes [Cp(CO)2FeCCArCCFe(CO)2Cp] {Cp= C5H5; 6a-g, Ar= C4H2S (a); 3-(C4H9)-C4HS (b); 3-(C16H33)-C4HS (c); C6H4 (d); 2,5-bis(OC4H9)-C6H2 (e); 2,5-bis(OC8H17)-C6H2 (f); (C6H4)2 (g)} was prepared by the three-step Pd-catalysed Extended-One-Pot (EOP) synthetic protocol from Bu3SnCCH, XArX (X=I,Br) and Cp(CO)2FeI. Complexes 6a,d,g were then exposed to ultraviolet irradiation in presence of an equivalent amount of 1,2-bis(diphenylphosphyne)ethane (dppe) to form the corresponding bimetallic complexes [Cp(dppe)FeCCArCCFe(dppe)Cp] (7a,d,g). Compounds 6a-g and 7a,d,g were characterised by Ciclic Voltammetry (CV). The most significant electrochemical information comes from the oxidation of the dppe derivatives. The E° separations between the subsequent reversible waves suggest that the efficiency of the metal-metal electronic coupling decreases in the order 6a > 6d > 6g. Complexes 7a and 7g were also chemically oxidised with [Fe(Cp*)]2[BF4] {Cp*= C5(CH3)5} and [Fe(Cp)]2[BF4] respectively, and the Near Infrared (NIR) spectra of the mixed valence species 7a+ and 7g+ were recorded. A strong Charge Transfer band (ICT) was observed only for the radical cation 7a+. While this finding confirms the existence of electronic interaction between the two termini when a 2,5-thiophene group is present in the spacer, the NIR spectrum of 7g+ reveals a reduced efficiency in conveying electrons when the C4H2S moiety is replaced by a 4,4'-biphenyl. In order to rationalise and quantify the extent of electronic communication, ruled by geometrical and electronic factors, Density Functional computational results on selected [Cp (PH3)2Fe and [Cp(CO)2Fe binuclear model complexes are reported

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Iron Acyl Complexes

Liebmann

Zastrow

Rück‐Braun

2014

Patai's Chemistry of Functional Groups

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This chapter covers a selection of acyl complexes and synthetic applications published within the past two decades. Iron acyl complexes are useful building blocks for organic synthesis. This survey covers recent synthetic applications of a selection of acyl complexes published within the last two decades. Herein, acyl complexes derived from carbonyl iron reagents are discussed, besides cyclopentadienyl dicarbonyl iron compounds, their phosphine‐substituted chiral‐at‐iron derivatives and diiron acyl complexes. This chapter has been organized according to the above classification with additional ligands and their reactivity, for example allyl, dienes.

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Convenient routes to mono- and dinuclear (C5Me5)iron(II) complexes bearing acyl, alkynyl, aryl and thienyl ligands

Cited by 9 publications

References 18 publications

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

A Joint Experimental and Computational Study on the Electronic Communication in Diethynylaryl‐Bridged (η⁵‐C₅H₅)Fe(η²‐dppe) and (η⁵‐C₅H₅)Fe(CO)₂ Units

Iron Acyl Complexes

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Convenient routes to mono- and dinuclear (C5Me5)iron(II) complexes bearing acyl, alkynyl, aryl and thienyl ligands

Cited by 9 publications

References 18 publications

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

Reactions of a Gallane(pyridyl)iron Complex with Internal and Terminal Alkynyl Esters: C−O and C−C Bond Cleavage and Oxidative Addition of C−H Bond

A Joint Experimental and Computational Study on the Electronic Communication in Diethynylaryl‐Bridged (η5‐C5H5)Fe(η2‐dppe) and (η5‐C5H5)Fe(CO)2 Units

Iron Acyl Complexes

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A Joint Experimental and Computational Study on the Electronic Communication in Diethynylaryl‐Bridged (η⁵‐C₅H₅)Fe(η²‐dppe) and (η⁵‐C₅H₅)Fe(CO)₂ Units