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Title: 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

Abstract

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 ofmore » 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%.« less

Authors:
; ; ;  [1]; ;  [2]
  1. Univ. of California at San Diego, La Jolla (USA)
  2. Ohio State Univ., Columbus (USA)
Publication Date:
OSTI Identifier:
7198677
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 111:13; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Loren, S D, Campion, B K, Heyn, R H, Tilley, D, Bursten, B E, and Luth, K W. 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. United States: N. p., 1989. Web. doi:10.1021/ja00195a026.
Loren, S D, Campion, B K, Heyn, R H, Tilley, D, Bursten, B E, & Luth, K W. 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. United States. doi:10.1021/ja00195a026.
Loren, S D, Campion, B K, Heyn, R H, Tilley, D, Bursten, B E, and Luth, K W. Wed . "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". United States. doi:10.1021/ja00195a026.
@article{osti_7198677,
title = {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},
author = {Loren, S D and Campion, B K and Heyn, R H and Tilley, D and Bursten, B E and Luth, K W},
abstractNote = {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%.},
doi = {10.1021/ja00195a026},
journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 111:13,
place = {United States},
year = {1989},
month = {6}
}