TMEDA in Iron‐Catalyzed Hydromagnesiation: Formation of Iron(II)‐Alkyl Species for Controlled Reduction to Alkene‐Stabilized Iron(0)

N,N,N’,N’‐Tetramethylethylenediamine (TMEDA) has been one of the most prevalent and successful additives used in iron‐catalysis, finding application in reactions as diverse as cross‐coupling, C‐H activation and borylation. However, the role that TMEDA plays in these reactions remains largely undefined. Herein, studying the iron‐catalyzed hydromagnesiation of styrene derivatives using TMEDA has provided molecular‐level insight into the role of TMEDA in achieving effective catalysis. Key is the initial formation of TMEDA‐iron(II) alkyl species which undergo a controlled reduction to selectively form catalytically active styrene‐stabilized iron(0)‐alkyl complexes. While TMEDA is not bound to the catalytically active species, these active iron(0) complexes cannot be accessed in the absence of TMEDA. This mode of action, allowing for controlled reduction and access to iron(0) species, represents a new paradigm for the role of this important reaction additive in iron catalysis

Mechanistic investigations of the Fe(ii) mediated synthesis of squaraines

The scission and homologation of CO is a fundamental process in the Fischer–Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. Mechanistic investigations, conducted using in situ monitoring and reaction sampling techniques (IR, NMR, EPR and Mössbauer spectroscopy) and structural characterisation of isolable species, identify a number of proposed intermediates. Crystallographic and IR spectroscopic data reveal a series of migratory insertion reactions from 1Mes to 4Mes. Further studies past the formation of 4Mes suggest that ketene complexes are formed en route to squaraine 2Mes and iron carboxylate 3Mes, with a number of ketene containing structures being isolated, in addition to the formation of unbound, protonated ketene (8). The synthetic and mechanistic studies are supported by DFT calculations

Изучение закономерностей формирования режимов электропотребления участков нефтепровода для оценки целевого показателя энергосбережения предприятий трубопроводного транспорта нефти

Тез. докл. VI Междунар. науч.-техн. конф. (науч. чтения, посвящ. П. О. Сухому), Гомель, 19–20 окт. 2006 г

Organometallic neptunium(III) complexes

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements

Insight into iron C-C cross-coupling catalysis through structure, bonding and mechanism

Thesis (Ph. D.)--University of Rochester. Dept. of Chemistry, 2017.Iron catalyzed C-C cross coupling reactions have drawn significant interest as more versatile and cost effective alternatives to traditional precious metal catalysts, however limited mechanistic understanding of these reactions has been reported hindering rational optimization of these systems. The use of electron paramagnetic resonance, magnetic circular dichroism, Mössbauer spectroscopy, and density functional theory, in addition to GC, NMR, and X-ray crystallography, are applied in the examination of structural and mechanistic aspects of in situ iron cross-coupling chemistry with a focus on elucidating how different nucleophiles, reaction additives and protocols affect reactivity. In Chapter 2 and 3, initial studies presented investigate iron-bisphosphine catalyzed cross-coupling of aryl nucleophiles with alkyl halides. These studies describe the iron species formed in situ and provide insight into the active species of catalysis as a function of nucleophile in both Kumada and Suzuki-Miyaura cross-coupling reactions. In Chapter 4, further studies investigate simple iron salt catalysts with methyl and ethyl Grignards for direct determination of iron species present in solution and their reactivity with electrophile. Additional studies further probe the effect of N-methylpyrrolidone as a co-solvent. In conclusion, it is shown in these studies the novel utility of these direct spectroscopic probes in monitoring in situ iron speciation and reactivity with electrophile. Furthermore, through monitoring of reactions we can also define why key aspects of the catalytic protocol are necessary for high yields and selectivities providing insight to guide rational optimization of these systems

CCDC 970891: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 971610: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 970889: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

Crystal structure of bromidopentakis(tetrahydrofuran-κO)magnesium bis[1,2-bis(diphenylphosphanyl)benzene-κ2P,P′]cobaltate(−1) tetrahydrofuran disolvate

Structural characterization of the ionic title complex, [MgBr(THF)5][Co(dpbz)2]·2THF [THF is tetrahydrofuran, C4H8O; dpbz is 1,2-bis(diphenylphosphanyl)benzene, C30H24P2], revealed a well-separated cation and anion co-crystallized with two THF solvent molecules that interact with the cation via weak C—H...O contacts. The geometry about the cobalt center is pseudotetrahedral, as is expected for a d10 metal center, only deviating from an ideal tetrahedral geometry because of the restrictive bite angles of the bidentate phosphane ligands. Three THF ligands of the cation and one co-crystallized THF solvent molecule are each disordered over two orientations. In the extended structure, the cations and THF solvent molecules are arranged in (100) sheets that alternate with layers of anions, the latter of which show various π-interactions, which may explain the particular packing arrangement