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
Journal Article
·
· Journal of the American Chemical Society; (United States)
- 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), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:26; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYLATED AROMATICS
AROMATICS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
EQUILIBRIUM
HYDRIDES
HYDROGEN COMPOUNDS
IONS
KINETICS
LATTICE PARAMETERS
LUTETIUM COMPLEXES
LUTETIUM COMPOUNDS
LUTETIUM HYDRIDES
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
RARE EARTH COMPLEXES
RARE EARTH COMPOUNDS
REACTION KINETICS
RESONANCE
SCATTERING
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
YTTRIUM COMPLEXES
YTTRIUM COMPOUNDS
YTTRIUM HYDRIDES
400201* -- Chemical & Physicochemical Properties
ALKYLATED AROMATICS
AROMATICS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
EQUILIBRIUM
HYDRIDES
HYDROGEN COMPOUNDS
IONS
KINETICS
LATTICE PARAMETERS
LUTETIUM COMPLEXES
LUTETIUM COMPOUNDS
LUTETIUM HYDRIDES
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
RARE EARTH COMPLEXES
RARE EARTH COMPOUNDS
REACTION KINETICS
RESONANCE
SCATTERING
THERMODYNAMICS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
YTTRIUM COMPLEXES
YTTRIUM COMPOUNDS
YTTRIUM HYDRIDES