Alkoxy and aryloxy derivatives of (pentamethylcyclopentadienyl)ruthenium. X-ray crystal structures of ((. eta. sup 5 -C sub 5 Me sub 5 )Ru(. mu. -OMe)) sub 2 , ((. eta. sup 5 -C sub 5 Me sub 5 )(CO)Ru(. mu. -OEt)) sub 2 , and (. eta. sup 5 -C sub 5 Me sub 5 )Ru(. eta. sup 5 -2,6- sup t Bu sub 2 C sub 6 H sub 3 O) and molecular orbital analysis of ((. eta. sup 5 -C sub 5 H sub 5 )Ru(. mu. -OMe)) sub 2

Journal Article · Wed Jun 21 00:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00195a026· OSTI ID:7198677

Loren, S D; Campion, B K; Heyn, R H; Tilley, D ^[1]; Bursten, B E; Luth, K W ^[2]

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1. Univ. of California at San Diego, La Jolla (USA)
2. Ohio State Univ., Columbus (USA)

Ruthenium methoxide dimer (Cp*Ru({mu}-OMe)){sub 2} (1, Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}) is produced by reaction of (Cp*RuCl{sub 2}){sub 2} or Cp*RuCl{sub 2}(pyr) with NaOMe in methanol or by reaction of CP* (PCy{sub 3})RuCl with LiOMe in methanol. Compound 1 is best prepared in pure form (in 84% yield) by reaction of the tetranuclear cluster (Cp*RuCl){sub 4} with 4 equiv of LiOMe in methanol. An X-ray crystallography study revealed that 1 has a dimeric structure with bridging methoxy ligands. The dimer is folded along the O{hor ellipsis}O axis, with a fold angle of 124.3{degree}. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.821 (8) {angstrom}, b = 6.659 (3) {angstrom}, c = 21.51 (1) {angstrom}, {beta} = 103.32 (3){degree}, Z = 8, V = 2,205 (2) {angstrom}{sup 3}, and R{sub F} = 2.17%. Ethoxide dimer (Cp*Ru({mu}-OEt)){sub 2} (2), prepared from (Cp*RuCl){sub 4} and LiOEt in ethanol, combines with carbon monoxide to form the adduct (Cp*(CO)Ru({mu}-OEt)){sub 2} (3). Compound 3 crystallizes in tetragonal space group P{anti 4}2{sub 1}C with a = 26.22 (2) {angstrom}, c = 8.709 (5) {angstrom}, Z = 8, V = 5,986 (6) {angstrom}{sup 3}, and R{sub F} = 5.68%. An analogous adduct of 1, (Cp*(CO)Ru({mu}-OMe)){sub 2} (4), is observed by {sup 1}H NMR but is unstable in solution, eventually decomposing to (Cp*Ru(CO)({mu}-CO)){sub 2}. Reaction of LiO-2,6-{sup t}bu{sub 2}c{sub 6}H{sub 3} with (Cp*RuCl){sub 4} in toluene gives the {eta}{sup 5}-oxocyclohexadienyl complex Cp*Ru({eta}{sup 5}-2,6-{sup t}Bu{sub 2}C{sub 6}H{sub 3}O) (5), which was crystallographically characterized. Compound 5 crystallizes in space group P2{sub 1}/n with a = 12.203 (3) {angstrom}, b = 10.028 (3) {angstrom}, c = 18.414 (4) {angstrom}, {beta} = 99.11 (2){degree}, Z = 4, V = 2,225 (1) {angstrom}{sup 3}, and R{sub F} = 3.03%.

• OSTI ID: 7198677
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 111:13; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
CRYSTAL STRUCTURE
DATA ANALYSIS
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
METALS
COMPLEXES
DATA
ELEMENTS
INFORMATION
NUMERICAL DATA
TRANSITION ELEMENT COMPLEXES
360104* - Metals & Alloys- Physical Properties
400201 - Chemical & Physicochemical Properties