Manipulation of organolanthanide coordinative unsaturation synthesis, structures, structural dynamics, comparative reactivity, and comparative thermochemistry of dinuclear. mu. -hydrides and. mu. -alkyls and (. mu. -R sub 2 Si(Me sub 4 C sub 5 )(C sub 5 H sub 4 )) sub 2 supporting ligation
- Northwestern Univ., Evanston, IL (United States)
This contribution describes lutetium and yttrium hydrocarbyl and hydride chemistry based upon the chelating R{sub 2}Si({eta}{sup 5}-C{sub 5}H{sub 4})({eta}{sup 5}-Me{sub 4}C{sub 5}){sup 2{minus}} ligand (R = Me, Et; abbreviated R{sub 2}SiCpCp{double prime}). The ligand is prepared by reaction of the corresponding R{sub 2}Si(CP{double prime})Cl derivative with NaC{sub 5}H{sub 5}. Subsequent metalation and reaction with MCl{sub 3}{center dot}3THF (M = Y, Lu) yields R{sub 2}SiCpCp{double prime}MCl{sub 2}{sup {minus}}Li(OEt{sub 2}){sub 2}{sup +} complexes, which in turn can be alkylated to yield R{sub 2}SiCpCp{double prime}MCHTMS{sub 2} derivatives (TMS = SiMe{sub 3}). Pertinent crystallographic data for Me{sub 2}SiCpCp{double prime}LuCHTMS{sub 2} at {minus}120C: P{ovr 1} (no. 2), z = 4, a = 16.049 (3) {angstrom}, b = 17.945 (4) {angstrom}, c = 8.993 (3) {angstrom}, {alpha} = 93.36 (2){degree}, {beta} = 90.92 (2){degree}, and {gamma} = 82.54 (2){degree}; R(F) = 0.030 for 6085 independent reflections with I > 3{sigma}(I). The structure is of a 'bent-sandwich' Cp{prime}MX-type (Cp{prime} = {eta}{sup 5}-Me{sub 5}C{sub 5}) with relaxed interligand nonbonded interactions vis-a-vis the Cp{prime}{sub 2}M and Me{sub 2}SiCP{double prime}M analogs (Lu-CHTMS{sub 2} = 2.365 (7) {angstrom}) and having one close Lu{center dot}{center dot}{center dot}MeSi (Lu-C = 2.820 (8) {angstrom}) secondary interaction. These alkyls initiate the polymerization of ethylene and undergo relatively slow hydrogenolysis to yield dihydrides of stoichiometry (R{sub 2}SiCpCp{double prime}MH){sub 2} via detectable intermediates of stoichiometry (R{sub 2}SiCpCp{double prime}){sub 2}M{sub 2}(H)(CHTMS{sub 2}). 90 refs.
- OSTI ID:
- 5731047
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 112:26; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
LUTETIUM COMPLEXES
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
YTTRIUM COMPLEXES
ALKYLATED AROMATICS
CHEMICAL REACTION KINETICS
EQUILIBRIUM
IONS
LATTICE PARAMETERS
LUTETIUM HYDRIDES
NUCLEAR MAGNETIC RESONANCE
ORGANIC SILICON COMPOUNDS
THERMODYNAMICS
X-RAY DIFFRACTION
YTTRIUM HYDRIDES
AROMATICS
CHARGED PARTICLES
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HYDRIDES
HYDROGEN COMPOUNDS
KINETICS
LUTETIUM COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
RARE EARTH COMPLEXES
RARE EARTH COMPOUNDS
REACTION KINETICS
RESONANCE
SCATTERING
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
YTTRIUM COMPOUNDS
400201* - Chemical & Physicochemical Properties