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 )

Journal Article · Mon Jan 01 00:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00115a015· OSTI ID:6620831

Bruce, M I; Hambley, T W; Liddell, M J; Snow, M R; Swincer, A G; Tiekink, E R.T. ^[1]

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1. Univ. of Adelaide (Australia)

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.

• OSTI ID: 6620831
• Journal Information: Organometallics; (USA), Vol. 9:1; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

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