766521-45-3Relevant academic research and scientific papers
Oxidative dimerization of aryldiynyl-ruthenium complexes
Bruce, Michael I.,Jevric, Martyn,Costuas, Karine,Gendron, Frederic,Halet, Jean-Francois,Skelton, Brian W.
, p. 6555 - 6566,12 (2012)
Chemical oxidation of Ru(C≡CC≡CR)(dppe)Cp with [FeCp 2]PF6 affords the binuclear cations [{Ru(dppe)Cp} 2C8R2]2+(PF6 -)2 (R = Ph, 72+(PF6 -)2; R = Fc, 82+(PF6 -)2) by radical coupling at electron-rich sites involving the inner and outer C≡C triple bonds, to give cyclobutenediylidene derivatives. In each case, mixtures of symmetrical and asymmetrical isomers were obtained (2:1 for 72+(PF6-)2, 1:1 for 82+(PF6-)2), shown by single-crystal X-ray diffraction structure determinations of 7 2+-asym(PF6-)2 and 8 2+-sym(AsF6-)2. 82+-sym consists of a central C4 ring with two =C=C=Ru(dppe)Cp groups in the 1,2-positions and two Fc substituents in the 3,4-positions, whereas for 7 2+-asym the substituent =Ru(dppe)Cp is in the 1-position, =C=C=Ru(dppe)Cp is in the 2-position, Ph is in the 3-position, and -C≡CPh is in the 4-position. DFT calculations reveal that the precursor cationic diynyl complexes show important electron density on Cβ and C δ, suggesting that radical coupling (Cδ + Cδ) or (Cβ + Cδ) affords the sym and asym isomers, respectively.
Synthesis, structures and some reactions of Ru(C≡CC≡CFc) (PP)Cp (PP=dppm, dppe) and related compounds
Bruce, Michael I.,de Montigny, Frédéric,Jevric, Martyn,Lapinte, Claude,Skelton, Brian W.,Smith, Mark E.,White, Allan H.
, p. 2860 - 2871 (2004)
The compounds Ru(C≡CC≡CFc)(PP)Cp [PP=dppe (1), dppm (2)], have been obtained from reactions between RuCl(PP)Cp and FcC≡CC≡CSiMe3 in the presence of KF (1) or HC≡CC≡CFc and K[PF6] (2), both with added dbu. The dppe complex reacts with Co2(CO)6 (L2)[L2=(CO)2, dppm] to give 3, 4 in which the Co2(CO)4 (L2) group is attached to the outer C≡C triple bond. The PPh 3 analogue of 3 (5) has also been characterised. In contrast, tetracyanoethene reacts to give two isomeric complexes 6 and 7, in which the cyano-olefin has added to either C≡C triple bond. The reaction of RuCl(dppe)Cp with HC≡CC≡CFc, carried out in a thf/NEt3 mixture in the presence of Na[BPh4], gave [Ru{C≡CC(NEt3)- CHFc}(dppe)Cp]BPh4 (8), probably formed by addition of the amine to an (unobserved) intermediate butatrienylidene [Ru(-C-C-C-CHFc)(dppe)Cp]+. The reaction of I2 with 8 proceeds via an unusual migration of the alkynyl group to the Cp ring to give [RuI(dppe) {η-C5H4 C≡CC(NEt3)-CHFc}]I3 (9). Single-crystal X-ray structural determinations of 1, 2 and 4-9 are reported. Published by Elsevier B.V.
