TITLE

Homobinuclear Ru-Ru and heterobinuclear Ru-Rh complexes with alkynyl and vinylidene ligands as molecular units

AUTHOR(S)
Werner, Helmut; Bachmann, Petra; Martin, Marta
PUB. DATE
May 2001
SOURCE
Canadian Journal of Chemistry;May2001, Vol. 79 Issue 5/6, p519
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The chelate complex [RuCl[sub 2] {κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ] (1) reacted, in the presence of CF[sub 3] SO[sub 3] Ag, with 1 equiv of C[sub 6] H[sub 4] (CºCH)[sub 2] -p (4) to afford the mononuclear vinylidene compound [RuCl(C=CHC[sub 6] H[sub 4] -p-CºCH){κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ](CF[sub 3] SO[sub 3] ) (3). From 1 and 0.5 equiv of 4, the binuclear bis(vinylidene) complex [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -p-CH=C)RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ](CF[sub 3] SO[sub 3] )[sub 2] (6) was obtained. The related compound [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m-CH=C)RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ](CF[sub 3] SO[sub 3] )[sub 2] (7) was prepared from 1, 0.5 equiv of C[sub 6] H[sub 4] (CºCH)[sub 2] -m (5), and silver triflate. The reaction of 2 or 3 with [RhCl(P-i-Pr[sub 3] )[sub 2] ][sub 2] (8) in the molar ratio of 2:1 yields, by addition of the 14-electron fragment [RhCl(P-i-Pr[sub 3] )[sub 2] ] to the uncoordinated C—C triple bond, the heterobinuclear complexes [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m/p-CºCH)RhCl(P-i-Pr[sub 3] )[sub 2] ](CF[sub 3] SO[sub 3] ) (9, 10) which slowly rearrange at room temperature to give the bis(vinylidene) isomers [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m/p-CH=C)RhCl(P-i-Pr[sub 3] )[sub 2] ](CF[sub 3] SO[sub 3] ) (11, 12).Key words: ruthenium, rhodium, vinylidene complexes, alkyne complexes, phosphine complexes.En présence de CF[sub 3] SO[sub 3] Ag, le chélate complexe [RuCl[sub 2] {κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ] (1) réagit avec un équivalent de C[sub 6] H[sub 4] (CºC)[sub 2] -p (4) pour conduire à la formation du composé vinylidène mononucléaire [RuCl(C=CHC[sub 6] H[sub 4] -p-CºC){κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ](CF[sub 3] SO[sub 3] )[sub 2] (3). À partir de 1 et d'un demi-équivalent de 4, on obtient le complexe bis(vinylidène) binucléaire [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -p-C=C)RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ] (CF[sub 3] SO[sub 3] )[sub 2] (6). On a préparé le composé apparenté [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m-C=C)RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] ] (CF[sub 3] SO[sub 3] )[sub 2] (7) en faisant réagir le composé 1 un demi-équivalent de C[sub 6] H[sub 4] (CºCH)[sub 2] -m (5) en présence de triflate d'argent. Par le biais d'une addition du fragment à quatorze électrons [RhCl(P-i-Pr[sub 3] )[sub 2] ] à la triple liaison qui n'est pas coordinée, les réactions des composés 2 ou 3 avec le [RhCl(P-i-Pr[sub 3] )[sub 2] ][sub 2] (8), dans un rapport molaire de 2:1, conduisent aux complexes hétérobinucléaires [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m/p-CºC)RhCl(P-i-Pr[sub 3] )[sub 2] ] (CF[sub 3] SO[sub 3] )[sub 2] (9, 10) qui se réarrangement lentement à la température ambiante pour conduire aux isomères bis(vinylidènes) [RuCl{κ[sup 2] (P,O)-i-Pr[sub 2] PCH[sub 2] CH[sub 2] OMe}[sub 2] (C=CHC[sub 6] H[sub 4] -m/p-C=C)RhCl(P-i-Pr[sub 3] )[sub 2] ] (CF[sub 3] SO[sub 3] )[sub 2] (11, 12).Mots clés : ruthénium, rhodium, complexes de vinylidènes, complexes d'alcynes, complexes de phosphines.[Traduit par la Rédaction]
ACCESSION #
10580664

 

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