0000000000221332
AUTHOR
Jean-claude Daran
A New Synthetic Method and Solution Equilibria for the Chlorotitanate( IV ) Anions − Evidence for the Existence of a New Species: [Ti 2 Cl 11 ] 3−
TiCl3 is oxidized by SOCl2 in the presence of the appropriate amount of [NEt3Bz]Cl or [PPN]Cl [Bz = benzyl; PPN = bis(triphenylphosphanyl)iminium] to afford the corresponding salts of [Ti2Cl9]−, [Ti2Cl10]2− or [TiCl6]2−. The results of cyclic voltammetric and solution IR studies in the Ti−Cl stretching region are interpreted in terms of a rapid chloride-redistribution equilibrium between [Ti2Cl10]2− on one side and a mixture of [Ti2Cl9]− and a previously unreported [Ti2Cl11]3− species on the other side. In the solid state, however, a compound with the [PPN]3[Ti2Cl11] stoichiometry exists as a mixture of [PPN]2[Ti2Cl10] and [PPN]2[TiCl6]. The PPN salt of [Ti2Cl9]− has been structurally chara…
The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts
The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…
Modular Phosphole-Methano-Bridged-Phosphine(Borane) Ligands. Application to Rhodium-Catalyzed Reactions
The synthesis of the phospholyl(phosphinoborane)methane air- and moisture-stable hybrid ligands 4a–f, starting from 1-phenylphospholes 1a–d, was performed via P–C bond coupling on the methano bridge. Two strategies were investigated, according to the phospholyl moiety used as a nucleophilic or an electrophilic reagent. In the first pathway, the phospholyl anions react with the easily available (chloromethyl)diphenylphosphine–borane 3 to afford ligands 4a–d in 29–67% isolated yields. In the second pathway, the phospholyl(dicyclohexylphosphinoborane)methane ligands 4e,f were synthesized in 18–23% yields, through a nucleophilic substitution on the cyanophosphole. Removal of the BH3 moiety on 4…
An easy route to 1-germaindenes via a transmetallation zirconiumgermanium reaction
Abstract Several 1-zirconaindenes ( 4 ) have been obtained easily by heating phenylmethylzirconocene with various symmetrical (R R′ CH 3 , C 2 H 5 , n-C 3 H 7 , Si(CH 3 ) 3 and unsymmetrical (R CH 3 , R′ Si(CH 3 ) 3 ) alkynes (RCCR′). Under similar experimental conditions, the ynamine, diethylaminotrimethylsilylethyne, led to a regioselective reaction. From the X-ray structure of the zirconaindene product, the trimethylsilyl group was found close to the zirconium atom. Compounds 4 with germanium tetrachloride afford new 1-germaindenes ( 7 ) characterized by 1 H and 13 C NMR and mass spectrometry, in good yield.
First Dibenzophospholyl(diphenylphosphino)methane−Borane Hybrid P−(η2-BH3) Ligand: Synthesis and Rhodium(I) Complex
The first dibenzophospholyl(diphenylphosphino)methane−borane hybrid ligand has been prepared from a Pd-catalyzed reaction of (chloromethyl)diphenylphosphine−borane with the dibenzophospholyl anion. This borane precursor is readily synthesized using a promising new reaction of diphenylphosphine−borane with dichloromethane, under phase transfer catalysis (PTC) conditions. The dibenzophospholyl(diphenylphosphino)methane−borane acts as a chelating P−(η2-BH3) ligand to afford an air-stable Rh(I) complex. The X-ray crystal structure of this complex shows complexation of both benzophospholyl and borane moieties.
Phospholylmethano P-chirogenic-phosphine-borane as P-(η2-BH3)-chelating ligands of rhodium (I): Synthesis, characterization and asymmetric hydrogenation
International audience; The stereoselective synthesis of new phospholylmethano P-chirogenic-phosphine-borane was achieved by P-C bond formation of the bridge, using electrophilic or nucleophilic P*-building blocks. These P1CH2P2*.BH3 ligands behaved as chelating (κ1-P1)-(η2-BH3) entities towards the cationic rhodium(I) centre. The resulting chiral rhodium complexes were tested in asymmetric rhodium catalyzed hydrogenation of methyl 2-(acetamido)acrylate.
New, Multi‐Dimensional Cu(tn)‐[M(CN) 6 ] n – Cyano‐Bridged, Bimetallic Coordination Materials (M = Fe II , Co III , Cr III and tn = 1,3‐Diaminopropane)
Reaction of the [Fe I I I (CN) 6 ] 3 - anion with [Cu I I (tn)(H 2 O) n ] 2 + (tn = 1,3-diaminopropane) affords the compounds [{Cu I I (tn)} 2 -{Fe I I (CN) 6 }].KCl.5H 2 O (1), [(Cu"(tn))2(Fe"(CN) 6 )].4H 2 O (2), and [{Cu I I (tnH) 2 (H 2 O) 2 }{Fe I I (CN) 6 }].2H 2 O (3). Each iron center in 1 and 2 is linked to six copper(II) ions by six cyanide bridges, while each copper ion is linked to three equivalent iron(II) ions. Despite these resemblances, the two compounds present large structural differences caused by two different orientations of the Cu-NC-Fe bridges: compound 1 has a 2D structure which can be described as successions of "Cu 4 Fe 3 " defective cubane units, while compound 2 …
CCDC 2034046: Experimental Crystal Structure Determination
Related Article: Christine Salomon-Bertrand, J��r��me Bayardon, Hugo Laur��ano, Sylvain Jug��, Jean-Claude Daran, Maryse Gouygou|2021|J.Organomet.Chem.|938|121753|doi:10.1016/j.jorganchem.2021.121753