skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )

Abstract

The chemistry of the first example of a {eta}{sup 4}(5e)-butadienyl complex is described. Reaction of (CpRu(NCMe)({eta}{sup 4}-C{sub 4}Ph{sub 4}))(BF{sub 4}) with K(BHBu{sub 3}{sup a}) affords CpRu{double bond}C(Ph)-{eta}{sup 3}-(C(Ph)C(Ph)CH(Ph)) (5), which was structurally identified by single-crystal X-ray crystallography. Compound 5 is triclinic, space group P{anti 1} (No. 2); a = 10.156 (5), b = 10.996 (5), c = 13.145 (6) {angstrom}, {alpha} = 112.12 (4), {beta} = 101.20 (4), {gamma} = 103.76 (4){degree}. The molecule contains an open-chain {eta}{sup 4}(5e)-butadienyl system, in which the CpRu fragment is double bonded to C(1) (Ru-C(1) = 1.896 (5) {angstrom}), the remaining three carbon ruthenium distances Ru-C(2) (2.204 (5) {angstrom}), Ru-C(3) (2.152 (4) {angstrom}), and Ru-C(4) (2.154 (6) {angstrom}) being appropriate for an {eta}{sup 3}-allyl system. A mechanism is proposed for the formation of 5 involving conrotatory ring-opening of an {eta}{sup 3}-cyclobutenyl intermediate carrying an endo hydrogen, which becomes a pseudo-syn hydrogen on the terminus of the C{sub 4} chain.

Authors:
; ; ; ; ; ;  [1]
  1. Univ. of Bristol (England)
Publication Date:
OSTI Identifier:
6429153
Resource Type:
Journal Article
Journal Name:
Organometallics; (USA)
Additional Journal Information:
Journal Volume: 9:5; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RUTHENIUM COMPLEXES; CRYSTAL STRUCTURE; REACTIVITY; SYNTHESIS; DATA ANALYSIS; EXPERIMENTAL DATA; MEASURING INSTRUMENTS; MEASURING METHODS; ORGANOMETALLIC COMPOUNDS; COMPLEXES; DATA; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Crocker, M, Green, M, Nagle, K R, Orpen, A G, Neumann, H P, Morton, C E, and Schaverien, C J. Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 ). United States: N. p., 1990. Web. doi:10.1021/om00119a012.
Crocker, M, Green, M, Nagle, K R, Orpen, A G, Neumann, H P, Morton, C E, & Schaverien, C J. Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 ). United States. https://doi.org/10.1021/om00119a012
Crocker, M, Green, M, Nagle, K R, Orpen, A G, Neumann, H P, Morton, C E, and Schaverien, C J. 1990. "Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )". United States. https://doi.org/10.1021/om00119a012.
@article{osti_6429153,
title = {Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )},
author = {Crocker, M and Green, M and Nagle, K R and Orpen, A G and Neumann, H P and Morton, C E and Schaverien, C J},
abstractNote = {The chemistry of the first example of a {eta}{sup 4}(5e)-butadienyl complex is described. Reaction of (CpRu(NCMe)({eta}{sup 4}-C{sub 4}Ph{sub 4}))(BF{sub 4}) with K(BHBu{sub 3}{sup a}) affords CpRu{double bond}C(Ph)-{eta}{sup 3}-(C(Ph)C(Ph)CH(Ph)) (5), which was structurally identified by single-crystal X-ray crystallography. Compound 5 is triclinic, space group P{anti 1} (No. 2); a = 10.156 (5), b = 10.996 (5), c = 13.145 (6) {angstrom}, {alpha} = 112.12 (4), {beta} = 101.20 (4), {gamma} = 103.76 (4){degree}. The molecule contains an open-chain {eta}{sup 4}(5e)-butadienyl system, in which the CpRu fragment is double bonded to C(1) (Ru-C(1) = 1.896 (5) {angstrom}), the remaining three carbon ruthenium distances Ru-C(2) (2.204 (5) {angstrom}), Ru-C(3) (2.152 (4) {angstrom}), and Ru-C(4) (2.154 (6) {angstrom}) being appropriate for an {eta}{sup 3}-allyl system. A mechanism is proposed for the formation of 5 involving conrotatory ring-opening of an {eta}{sup 3}-cyclobutenyl intermediate carrying an endo hydrogen, which becomes a pseudo-syn hydrogen on the terminus of the C{sub 4} chain.},
doi = {10.1021/om00119a012},
url = {https://www.osti.gov/biblio/6429153}, journal = {Organometallics; (USA)},
issn = {0276-7333},
number = ,
volume = 9:5,
place = {United States},
year = {Tue May 01 00:00:00 EDT 1990},
month = {Tue May 01 00:00:00 EDT 1990}
}