Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

Technical Report · Fri Nov 01 04:00:00 EST 1991

DOI:https://doi.org/10.2172/5698904· OSTI ID:5698904

Matsunaga, P T

The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

• Research Organization: Lawrence Berkeley Lab., CA (United States)
• Sponsoring Organization: DOE; USDOE, Washington, DC (United States)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5698904
• Report Number(s): LBL-31491; ON: DE92010300
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTIONS
COMPLEXES
COPPER COMPLEXES
DIMENSIONS
ELECTRON TRANSFER
LENGTH
MAGNETIC PROPERTIES
MAGNETIC SUSCEPTIBILITY
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHYSICAL PROPERTIES
RARE EARTH COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES
YTTERBIUM COMPLEXES