A. A. Koridze

Reactions of 1,4-difeffocenylbuta-1,3-diyne and 1,4-diphenylbut-l-en-3-yne with Ru3(CO)12. Crystal structure of Ru3(CO)8(μ3-η-1-η1-η4-η2-C4Ph2(CH=CHPh)2)

Diyne FcCmCC.CFc (Fc is ferrocenyl) reacts with Ru3(CO)12 in boiling hexane to yield binuclear complexes Ru2 and Ru2(CO)6(C4Fc2(C=CFc)2C=O) containing ruthenacyclopentadiene and diruthenacycloheptadienone rings, respectively. The isomerism of the complexes is due to the different ways of coupling of the alkyne fragments of the diyne, namely, “head-to-head”, “head-to-tail” or “tail-to-tail”. The reaction of enyne PhC=CCH=CHPh with Ru3(CO)12 under similar conditions gives isomeric binuclear complexes Ru2(CO)6(C4Ph2(CH=CHPh)2) and trinuclear clusters Ru3(CO)6(w-CO)2(C4Ph2(CH=CHPh)2) and Ru3(CO)8(μ3-,η1-η1-η4-η2 C4Ph2(CH=CHPh)2). The structure of the latter was determined by X-ray diffraction analysis. The Ru3 triangle coordinates eight terminal CO groups and the organic ligand resulting from the “head-to-head” dimerization of enyne molecules; the ruthenacyclopentadiene moiety is η4-coordinated to the Ru(CO)2 group, and the third ruthenium atom is η2-bound to one of the PhCH=CH groups.

Chirality, diastereotopism and structure of α-metallocenylcarbenium ions investigated by nmr spectroscopy

Abstract 1-Metallocenyl-2-methylpropyl cations are found to be chiral using nuclei diastereotopism. The positive charge distribution over the cations and the effect of a central metal atom (iron, ruthenium, osmium) are discussed.

(1,3-Diformylindenyl)cyclopentadienyl ruthenium derivatives

The reaction of [CpRu(CH3CN)3][PF6], [Cp*RuCl]n, and [CpFRuCl]n with 1,3-diformylindene results in the predominant formation of zwitter-ionic arene-cyclopentadienyl complexes {η6-1,3-(CHO)2C9H5}RuCp (Cp = C5H5), {η6-1,3-(CHO)2C9H5}RuCp* (Cp* = C5Me5), and {η6-1,3-(CHO)2C9H5}RuCpF (CpF = C5Me4CF3), respectively. The ruthenocenes {η5-1,3-(CHO)2C9H5}RuCp, {η5-1,3-(CHO)2C9H5}RuCp*, and {η5-1,3-(CHO)2C9H5}RuCpF were synthesized by the reaction of 1,3-diformylindenyl potassium with [CpRu(CH3CN)3][PF6], [Cp*RuCl]n, and [CpFRuCl]n.

Homoannular disubstituted ruthenocenes containing a trifluoromethyl(tetramethyl)cyclopentadienyl ligand

The reaction of the divalent ruthenium complexes [CpFRuCl]n and [CpFRu(MeCN)3]PF6 with substituted pentafulvenes 1,2-(Me2NCH)(CO2Et)C5H3 and 1,3-(Me2NCH)(CO2Et)- C5H3 followed by hydrolysis affords new homoannular disubstituted ruthenocenes {1,2- (CO2Et)(CHO)C5H3}RuCpF and {1,3-(CO2Et)(CHO)C5H3}RuCpF (CpF = C5Me4CF3), re- spectively.

Reactions of Silylalkynes with Triosmium and Triruthenium Clusters

Our continuing interest in transformations of heteroatom-substituted alkynes on transition metal clusters [1,2] has prompted us to investigate reactions of silylalkynes with triruthenium and triosmium clusters.

Reduction of (1,3-diformylindenyl)cyclopentadienylruthenium derivatives

The reduction of the (1,3-diformylindenyl)cyclopentadienylruthenium derivatives {η5-1,3-(CHO)2C9H5}RuCp (Cp = C5H5), {η5-1,3-(CHO)2C9H5}RuCp* (Cp* = C5Me5), and {η5-1,3-(CHO)2C9H5}RuCpF (CpF = C5Me4CF3) with NaBH4 or LiAlH4 under mild conditions affords the [1,3-bis(hydroxymethyl)indenyl]cyclopentadienylruthenium complexes {η5-1,3-(CH2OH)2C9H5}RuCp, {η5-1,3-(CH2OH)2C9H5}RuCp*, and {η5-1,3-(CH2OH)2C9H5}-RuCpF, respectively, in good yields.