RESUMEN
NHC-phosphinidene (NHCP) adducts are an emerging class of ligands with proven binding ability for main group and transition metal elements. They possess electron-rich P atoms with two lone pairs (LPs) of electrons, making them interesting platforms for the formation of multimetallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHCP)s, starting from alkylidene-bridged bis(NHC)s ((IMe)2CnH2n; n = 1,3) and triphosphirane (PDip)3 (Dip = 2,6-iPr2C6H3) as phosphinidene transfer reagent. The coordination chemistry of [{DipP(IMe)}2CH2], 1, was studied in detail, and complexes [1·FeBr2] and [1·Rh(cod)]Cl were prepared, showing that the ligand has a flexible bite angle. The dicarbonyl complex [1·Rh(CO)2]Cl, with an average value for the CO stretching frequency of 2029 cm-1, indicates a strongly donating ligand when compared to related complexes. The binding ability of the remaining two phosphorus LPs was demonstrated with AuCl(SMe2), giving the heterotrimetallic complex [1·(AuCl)2·Rh(cod)]Cl. Moreover, [1·Rh(cod)]X (X- = Cl, B(3,5-(CF3)2-C6H3)4) was tested in the catalytic hydrogenation of methyl-Z-α-acetamidocinnamate (MAC) and dimethyl itaconate (ItMe2), revealing that the chloride complex was inactive, while the BArF complex demonstrated moderate activity. Additionally, [1·Rh(cod)]Cl was shown to be moderately air- and moisture-stable, slowly decomposing to the corresponding NHC-stabilized bis-dioxophosphorane, which was independently synthesized by treating the free ligand with dry O2.
RESUMEN
A nickel complex incorporating an N2 O ligand with a rare η2 -N,N'-coordination mode was isolated and characterized by X-ray crystallography, as well as by IR and solid-state NMR spectroscopy augmented by 15 N-labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid-state structure. Computational studies revealed that η2 -N2 O binds to nickel slightly stronger than η2 -CO2 in this case, and comparably to or slightly stronger than η2 -CO2 to transition metals in general. Comparable transition-state energies for the formation of isomeric η2 -N,N'- and η2 -N,O-complexes, and a negligible activation barrier for the decomposition of the latter likely account for the limited stability of the N2 O complex.
RESUMEN
Chelating ligands have had a tremendous impact in coordination chemistry and catalysis. Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Herein, we describe a chelating, C2-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, which was isolated as a racemic mixture. The isolation and structural characterization of its isostructural, pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides featuring eight-membered metallacycles demonstrates the binding ability of the bis(carbene). Reduction of the nickel(II) dibromide with potassium graphite produces a dicoordinate nickel(0) complex that features one of the narrowest angles measured in any unsupported dicoordinate transition metal complexes.
RESUMEN
Isomeric bis(aldiminium) salts with a 1,4-cyclohexylene framework were synthesized. The first isolable bis(CAAC) was prepared from the trans-stereoisomer and its ditopic ligand competency was proven by conversion to iridium(I) and rhodium(I) complexes. Upon deprotonation, the cis-isomer yielded an electron rich olefin via a classic, proton-catalyzed pathway. The CîC bond formation from the desired cis-bis(CAAC) was shown to be thermodynamically very favorable and to involve a small activation barrier. Compounds that can be described as insertion products of the cis-bis(CAAC) into the E-H bonds of NH3, CH3CN and H2O were also identified.