DIVALENT LANTHANIDE CHEMISTRY; BIS (PENTAMETHYLCYCLOPENTADIENYL) EUROPIUM(II) AND YTTERBIUM(II) DERIVATIVES: CRYSTAL STRUCTURE OF BIS(PENTAMETHYLCYCLOPENTADIENYL) YTTERBIUM (II)TETRAHYDROFURAN HEMI (TOLUENE) AT 176K

Journal Article · Tue Apr 01 04:00:00 EST 1980 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic50212a031· OSTI ID:1030602

Tilley, T Don; Andersen, Richard A; Spencer, Brock; Ruben, Helena; Zalkin, Allan; Templeton, David H

Red, paramagnetic ({mu}{sub B} = 7.99 B.M., 5-50K) bis(pentamethylcyclopentadienyl) europium (II)(tetrahydrofuran)(diethylether), (Me{sub 5}C{sub 5}){sub 2}Eu(THF)(Et{sub 2}O) is isolated from reaction of three molar equivalents of sodium pentamethylcyclopentadienide and europium trichloride in refluxing tetrahydrofuran, after crystallization from diethyl ether. The monotetrahydrofuran complex, (Me{sub 5}C{sub 5}){sub 2}Eu(THF), may be isolated by use of toluene rather than diethyl ether as the crystallization solvent. Red, diamagnetic bis(pentamethylcyclopentadienyl)ytterbium(II)(tetrahydrofuran) is isolated from the reaction of ytterbium dichloride and sodium pentamethylcyclopentadienide in refluxing tetrahydrofuran. The diethyl ether complex, (Me{sub 5}C{sub 5}){sub 2}Yb(OEt{sub 2}), may be isolated by crystallization of the tetrahydrofuran complex from diethylether, The hemi-toluene complex, (Me{sub 5}C{sub 5}){sub 2} Yb(THF) {center_dot} 1/2 toluene, can be isolated by recrystallization of the tetrahydrofuran complex from toluene. As these divalent metallocenes are the first hydrocarbon-soluble lanthanide derivatives to be isolated we have examined the latter complex by X-ray crystallography. Crystals of (Me{sub 5}C{sub 5}){sub 2}Yb(OC{sub 4}H{sub 8}) {center_dot} 1/2(C{sub 6}H{sub 5}cH{sub 3}) crystalline in the monoclinic system, P2{sub 1}/n, with a = 11.358(8) {angstrom}, b = 21.756(19) {angstrom}, c = 10.691(7) {angstrom}, and {beta} = 101.84(5){sup o} at 176K. For Z = 4 the calculated density is 1.37 g cm{sup -3}. The ytterbium atom is coordinated to the oxygen atom of a tetrahydrofuran molecule and to two pentamethyl cyclopentadienyl rings. The molecule has approximate c{sub 2} symmetry about the Yb-0 bond. The Yb-0 distance is 2.41 {angstrom}, the Yb-C distances average 2.66 {angstrom}, and the Yb-Cp (centroid) distances average 2.37 {angstrom}. The Me{sub 5}C{sub 5} rings are in a staggered configuration with respect to each other. The methyl groups of the Me{sub 5}C{sub 5} groups are displaced by .03 to .21 {angstrom} from the planes of the five-membered rings away from the ytterbium atom. The toluene molecule is not coordinated to the complex and is on a center of symmetry in a disordered configuration. The 3466 data with F{sup 2} > 3{sigma} refined by full matrix least-squares to a conventional R factor of 0.036.

• Research Organization: Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
• Sponsoring Organization: Materials Sciences Division
• DOE Contract Number: AC02-05CH11231
• OSTI ID: 1030602
• Report Number(s): LBL-10490
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 19; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
36 MATERIALS SCIENCE
99 GENERAL AND MISCELLANEOUS
A CENTERS
ATOMS
CHEMISTRY
CONFIGURATION
CRYSTAL STRUCTURE
CRYSTALLIZATION
CRYSTALLOGRAPHY
ETHYL ETHER
EUROPIUM
OXYGEN
R FACTORS
RARE EARTHS
RECRYSTALLIZATION
SODIUM
SYMMETRY
TETRAHYDROFURAN
TOLUENE
YTTERBIUM