Cyclopentadienyliron dicarbonyl dimer: A simple tool for the hydrosilylation of aldehydes and ketones under air

International audienceThe readily available iron complex [CpFe(CO)2]2 (1) exhibits good catalytic activity in the hydrosilylation of aldehydes and ketones in the presence of diethoxymethylsilane. The procedure described is air-tolerant and applicable to a wide range of substrate

Synthesis, reactivity, and some photochemistry of ortho-N,N-dimethylaminomethyl substituted aryl and ferrocenyl pentamethylcyclopentadienyl dicarbonyl iron complexes

Supplementary materials: CCDC 928736, 928273, 928738, 928275, 928274 and 928737 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cifInternational audienceOrtho-lithiated N,N-dimethylaminomethyl ferrocene and benzyldimethylamine react with Cp*Fe(CO)2I to give the new complexes ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp) and Cp*Fe(CO)2-C6H4(o-CH2NMe2). Access to a wide variety of alkoxy-substituted complexes ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) can be easily achieved by tandem quaternization/alcoholysis of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp). Preliminary results show that chelated complexes can be obtained by displacement of one of the carbonyl ligands by photolysis. Crystal structures of ((Cp*Fe(CO)2)-2-(CH2NMe2)C5H3)Fe(Cp), ((Cp*Fe(CO)2)-2-(CH2OR)C5H3)Fe(Cp) (R = Ph, Bz, CHPh2 and d-menthyl) and [Cp*Fe(CO)2-C6H4(o-CH2NMe2)][I] are reported

Donor-substituted triaryl-1,3,5-triazinanes-2,4,6-triones: octupolar NLO-phores with a remarkable transparency-nonlinearity trade-off

International audienceWe report in this letter the measurement of the hyperpolarizabilities of a series of donor-substituted triaryl-1,3,5-triazinanes-2,4,6-triones by hyper Rayleigh scattering (HRS). A remarkable transparency-nonlinearity trade-off is evidenced for these octupolar NLO-phores which might be accessed in a straightforward synthetic way and in a few steps from commercial isocyanates

[Fp*Fc][PF6]: A remarkable non-symmetric dinuclear cation in a very stable mixed-valent state

We report herein dicarbonyl(pentamethylcyclopentadienyl)(ferroceniumyl)iron hexafluorophosphate, which contains a dimetallic cation with a remarkably stable mixed-valent (MV) structure and unexpected redox features. The electronic structure of this compound is discussed in the light of the existing Hush model, which suggests an unusually strong electronic coupling between the two iron centers, despite the non-symmetric environment of the metallic centers. End-to-end charge delocalization is not the main contributor to the extra-large stability of this MV complex, which originates from electronic effects other than the energetic difference between the two MV redox isomers (ΔG0). This open-shell derivative has also been briefly tested as a catalyst in the reductive etherification of aldehydes by hydrosilanes.G.G. thanks Region Bretagne for partial support of a PhD scholarship. The CNRS (PICS programs N 5676 and 7106) & ANR (2010- BLAN-7191) are acknowledged for financial support. M.G.H. thanks the ARC for financial support and an Australian Professorial Fellowship. O. Mongin (UMR 6226, Rennes) is acknowledged for experimental assistance and J.-F. Meunier (LCC, Toulouse) for recording the Mossbauer spectra

Mild and efficient rhodium-catalyzed deoxygenation of ketones to alkanes

International audienceA new and simple method for the deoxygenation of ketones to alkanes is presented. Most substrates are reduced under mild conditions by triethylsilane in the presence of catalytic amounts of [Rh(-Cl)(CO)2]2. This system selectively provides the methylene hydrocarbons in good to excellent yields starting from acetophenones and diaryl ketones. A rapid examination of the reaction pathway suggests that the ketone is first converted in alcohol which then undergoes hydrogenolysis to give the alkane

Rhodium-Catalyzed Direct Reductive Amination of Aldehydes and Ketones with Hydrosilanes

International audienceThe commercially available chlorodicarbonylrhodium(I) dimer was shown to be a highly active catalyst in the hydrosilylation of aldimines and ketimines under mild conditions. From these initial results, new procedures for the direct reductive amination of aldehydes and ketones employing this rhodium complex were developed with various primary and secondary amines in the presence of hydrosilanes

One-Pot Synthesis of Mononuclear Iron Alkynyl Complexes by Photolysis

International audienceA new access to organoiron complexes of type (dppe)Cp*Fe−C≡C−Ar (3) from the easily prepared precursor (CO)2Cp*FeCl (5) is described. This direct one-pot transformation realized upon UV irradiation is illustrated by various aromatic alkynes. A mechanism is also proposed for this reaction via the key intermediate [(dppe)Cp*Fe(CO)][PF6] (6)

Synthesis of new triphenylphosphines with pending ethynyl substituents

International audienceThe straightforward isolation and characterization of new triphenylphosphines possessing a pendent ethynyl substituent on one or several peripheral aryl ring(s) are reported. The synthesis of this family of compounds is achieved by retro-Favorsky reactions from the corresponding propargylic alcohol derivatives, themselves obtained following a classic Sonogashira-type coupling between the ad hoc bromophenyl phosphines and 2-methylbut-3-yn-2-ol

First application of chiral phosphotriesters in asymmetric metal catalysis: enantioselective Zn-catalyzed hydrosilylation of ketones in the presence of BINOL-derived phosphates

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