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Title: Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 )

Abstract

Reactions between Ru(C{sub 2}Me)(PPh{sub 3}){sub 2}({eta}-C{sub 5}H{sub 5}) or Ru(C{sub 2}Ph)(L){sub 2}({eta}-C{sub 5}H{sub 5}) (L{sub 2} = (PPh{sub 3}){sub 2}, dppe, (CO)(PPh{sub 3})) and (CF{sub 3}){sub 2}C=C(CN){sub 2} gave the corresponding {sigma}-cyclobutenyl complexes, of which Ru(C=CPhC(CF{sub 3}){sub 2}C(CN){sub 2})(CO)(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) (1g) was fully characterized by X-ray crystallography. Thermal isomerization of the dppe and (CO)(PPh{sub 3}) complexes to the {sigma}-buta-1,3-dien-2-yl derivatives occurred; under CO, two isomers of Ru(C(=C(CN){sub 2})CMe=C(CF{sub 3}){sub 2})(CO)(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) were formed. The X-ray structures of one of these (2h), and the phenyl analogue (2g), were determined. The allyls Ru({eta}{sup 3}-C(CF{sub 3}){sub 2}CXC=C(CN){sub 2})(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) (X = Me (3d), Ph (3g)) were obtained thermally or photochemically; the structure of 3g was also determined, thus completing the series {sigma}-cyclobutenyl, {sigma}-butadienyl, {eta}{sup 3}-allyl derived from the same metal/ligand combinations. Crystal data for 1g: orthorhombic, space group P2{sub 1}2{sub 1}2{sub 1}, a = 10.409 (2) {angstrom}, b = 16.227 (3) {angstrom}, c = 20.000 (3) {angstrom}, Z = 4; 2,851 data were refined to R = 0.040, R{sub w} = 0.041. Crystal data for 2g; monoclinic, space group P2{sub 1}/n, a = 14.942 (1) {angstrom}, b = 13.413 (2) {angstrom}, c = 16.928 (6) {angstrom}, {beta}more » = 97.02 (1){degree}, Z = 4; 3,659 data were refined to R = 0.045, R{sub w} = 0.059. Crystal data for 2h: monoclinic, space group C2/c, a = 22.237 (4) {angstrom}, b = 18.648 (5) {angstrom}, c = 17.731 (3) {angstrom}, {beta} = 124.93 (2){degree}, Z = 8; 3,076 data were refined to R = 0.039, R{sub w} = 0.042.« less

Authors:
; ; ; ; ;  [1]
  1. (Univ. of Adelaide (Australia))
Publication Date:
OSTI Identifier:
6620831
Alternate Identifier(s):
OSTI ID: 6620831
Resource Type:
Journal Article
Resource Relation:
Journal Name: Organometallics; (USA); Journal Volume: 9:1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RUTHENIUM COMPLEXES; CRYSTAL STRUCTURE; ACETYLATION; DATA ANALYSIS; EXPERIMENTAL DATA; MEASURING INSTRUMENTS; MEASURING METHODS; TRANSITION ELEMENT COMPLEXES; ACYLATION; CHEMICAL REACTIONS; COMPLEXES; DATA; INFORMATION; NUMERICAL DATA 400200* -- Inorganic, Organic, & Physical Chemistry

Citation Formats

Bruce, M.I., Hambley, T.W., Liddell, M.J., Snow, M.R., Swincer, A.G., and Tiekink, E.R.T. Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 ). United States: N. p., 1990. Web. doi:10.1021/om00115a015.
Bruce, M.I., Hambley, T.W., Liddell, M.J., Snow, M.R., Swincer, A.G., & Tiekink, E.R.T. Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 ). United States. doi:10.1021/om00115a015.
Bruce, M.I., Hambley, T.W., Liddell, M.J., Snow, M.R., Swincer, A.G., and Tiekink, E.R.T. Mon . "Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 )". United States. doi:10.1021/om00115a015.
@article{osti_6620831,
title = {Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 )},
author = {Bruce, M.I. and Hambley, T.W. and Liddell, M.J. and Snow, M.R. and Swincer, A.G. and Tiekink, E.R.T.},
abstractNote = {Reactions between Ru(C{sub 2}Me)(PPh{sub 3}){sub 2}({eta}-C{sub 5}H{sub 5}) or Ru(C{sub 2}Ph)(L){sub 2}({eta}-C{sub 5}H{sub 5}) (L{sub 2} = (PPh{sub 3}){sub 2}, dppe, (CO)(PPh{sub 3})) and (CF{sub 3}){sub 2}C=C(CN){sub 2} gave the corresponding {sigma}-cyclobutenyl complexes, of which Ru(C=CPhC(CF{sub 3}){sub 2}C(CN){sub 2})(CO)(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) (1g) was fully characterized by X-ray crystallography. Thermal isomerization of the dppe and (CO)(PPh{sub 3}) complexes to the {sigma}-buta-1,3-dien-2-yl derivatives occurred; under CO, two isomers of Ru(C(=C(CN){sub 2})CMe=C(CF{sub 3}){sub 2})(CO)(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) were formed. The X-ray structures of one of these (2h), and the phenyl analogue (2g), were determined. The allyls Ru({eta}{sup 3}-C(CF{sub 3}){sub 2}CXC=C(CN){sub 2})(PPh{sub 3})({eta}-C{sub 5}H{sub 5}) (X = Me (3d), Ph (3g)) were obtained thermally or photochemically; the structure of 3g was also determined, thus completing the series {sigma}-cyclobutenyl, {sigma}-butadienyl, {eta}{sup 3}-allyl derived from the same metal/ligand combinations. Crystal data for 1g: orthorhombic, space group P2{sub 1}2{sub 1}2{sub 1}, a = 10.409 (2) {angstrom}, b = 16.227 (3) {angstrom}, c = 20.000 (3) {angstrom}, Z = 4; 2,851 data were refined to R = 0.040, R{sub w} = 0.041. Crystal data for 2g; monoclinic, space group P2{sub 1}/n, a = 14.942 (1) {angstrom}, b = 13.413 (2) {angstrom}, c = 16.928 (6) {angstrom}, {beta} = 97.02 (1){degree}, Z = 4; 3,659 data were refined to R = 0.045, R{sub w} = 0.059. Crystal data for 2h: monoclinic, space group C2/c, a = 22.237 (4) {angstrom}, b = 18.648 (5) {angstrom}, c = 17.731 (3) {angstrom}, {beta} = 124.93 (2){degree}, Z = 8; 3,076 data were refined to R = 0.039, R{sub w} = 0.042.},
doi = {10.1021/om00115a015},
journal = {Organometallics; (USA)},
number = ,
volume = 9:1,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 1990},
month = {Mon Jan 01 00:00:00 EST 1990}
}