V. I. Zdanovich

Coupling and annelation of two acetylide groups and alkyne molecules in the reaction of (OC)5ReCCPh with ferrocenylacetylene. Crystal and molecular structure of Re2(CO)7{C8H2Ph2(C5H4FeC5H5)2} · acetone

X-Ray diffraction study was carried out of the binuclear complex Re2(CO)7(C8)H2Ph2Fc2) (II), obtained in the reaction of (OC)5ReCCPh with ferrocenylacetylene FcCCH in refluxing toluene. Complex II crystallizes in the monoclinic space group P 21/n with a 20.363(5), b 10.121(2), c 22.952(7) A, β 112.49(2)°, V 4302(2) A3, and Z = 4. Compound II possesses a rhenacyclopentadiene ring, fused with the methylenecyclopentene moiety along the central CC bond, and π-bonded by the Re (CO)3 group. The hydrocarbon ligand of compound II is formed by condensation of two PhCC groups and two FcCCH molecules. Preparative methods of synthesis of (OC)5ReCCPh, (OC)5ReCCCO2Me and (OC)5ReCCSiMe3 are reported.

Metallotropic rearrangement of η5-fluoroenyltricarbonyl-manganese in acid media

Abstract Using IR and PMR spectroscopy, it has been shown that on addition of trifluoroacetic acid to (η 5 -C 13 H 9 )Mn(CO) 3 in CH 2 Cl 2 solution protonation of position 9 of the fluorenyl ligand takes place with simultaneous migration of the metal atom onto the six-membered ring of the fluorenyl ligand, forming of [(η 6 -C 13 H 10 )Mn(CO) 3 ] + .

IR study of rotational isomerism in dirhenium and diruthenium complexes of the ferrole type

Abstract A novel type of rotational isomerism was found in binuclear dirhenium complex of ferrole type Re2(CO)7(C8H7Ph2Fc2) (II) by Fourier transform IR spectroscopy in a wide temperature range (165–293 K) in pentane and liquid xenon solutions. The conformers result from internal rotation of a metal carbonyl moiety about the multicentred bond involving another metal carbonyl fragment. According to IR and Raman spectroscopy, the diruthenium complex Ru2(CO)6{C4Fc2(CCFc)2} (III) exists in the solid state and in solution as two different conformers. In the solid state the ‘non-sawhorse’ conformation with the semibridging carbonyl group was found, which transforms in solution to the conformation containing only terminal carbonyl groups.

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

The redox properties of the clusters Ru3(CO)12(1), Ru3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(CO)9 (2), OS3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(CO)9 (3), Ru4(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(CO)12 (4), and RuOS3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(CO)12 (5) in THF have been studied by cyclic voltammetry in the temperature range from −60 to +20°C. It was demonstrated that reversible one-electron oxidation of the ferrocenyl fragment in clusters 2–5 occurs at more positive potentials (δE0=0.15–0.26 V) than that of free ferrocene. This is indicative of the electron-withdrawing character of the cluster core with respect to the ferrocenylacetylide ligand. The electron-withdrawing effect of the metal core is more pronounced in tetranuclear clusters4 and 5 than in trinuclear clusters2 and3. Unlike complexes1–3, which undergo irreversible reduction, complexes4 and5 undergo reversible one-electron reduction to form the corresponding radical anions4− and5−.

Metallotropic η5→η6 rearrangement in indenyltricarbonyl complexes of manganese and rhenium in an acid medium

An IR spectroscopic study has shown that the reactions of (η5-C9H7)M(CO)3 (M = Mn, Re) and (η5-C13H9)Mn(CO)3 with AlCl3·HCl and FSO3H involve metallotropic η5 → η6 rearrangement in which the metal carbonyl group migrates from the five- to the six-membered ring of the aromatic ligand. The reverse η6 → η5 rearrangement is initiated by bases.

Competitive metalation of η5-indenyl- and η5-cyclopentadienyltricarbonyl complexes of manganese and rhenium

Abstract Competitive metalation of the η 5 -indenyl- and η 5 -cyclopentadienyl-tricarbonyl complexes of manganese and rhenium by n-butyllithium in THF has been carried out and subsequent treatment of the lithium derivatives with trimethylchlorosilane has been performed. The following mixtures of compounds have been investigated: η 5 -C 9 H 7 Mn(CO) 3 and η 5 -C 5 H 5 Mn(CO) 3 , η-C 9 H 7 Re(CO) 3 and η 5 -C 5 H 5 Re(CO) 3 , η 5 -C 9 H 7 Mn(CO) 3 and η 5 -C 9 H 7 Re(CO) 3 , η 5 -C 5 H 5 Mn(CO) 3 and η 5 -C 5 H 5 Re(CO) 3 . It was shown that η 5 -C 9 H 7 Mn(CO) 3 and η 5 -C 5 H 5 Mn(CO) 3 do not undergo metalation in the presence of the corresponding complexes of rhenium. On metalation η 5 -indenyl and η 5 -cyclopentadienyl ligands coordinated to the same metal differ slightly in reactivity. The trimethylsilyl derivatives of the η 5 -indenyltricarbonyl complexes of manganese and rhenium were isolated as a mixture of two isomers in approximately equal amounts.

Reactions of the Ru3(CO)10(μ-Ph2PCH2PPh2) cluster with enynes RCH=CHC≡CR (R is phenyl or ferrocenyl). Formation of indenone derivatives of triruthenium clusters

The thermal reaction of Ru3(CO)10(μ-Ph2PCH2PPh2) (1) with enyne PhCH=CHC≡CPh afforded the trinuclear ruthenium clusters Ru3(CO)6{μ3-P(Ph)CH2PPh2}{μ3-C(Ph)=CHCC(Ph)(1,2-C6H4)C(=0)} (2), Ru3(μ-H)(CO)5{μ3-P(Ph)CH2PPh2}{μ3-C(Ph)=CHCC(Ph)(1,2-C6H4)C(—0)} (3), and Ru3(CO)6(μ-CO){μ3-P(Ph)CH2PPh2}{μ3-C(C=CPh2)CH=C(H)Ph} (4) and also two isomers of Ru3(CO)5(μ-CO)(μ-Ph2PCH2PPh2){μ3-C4Ph2(CH=CHPh)2} (5a and 5b). Clusters 2, 3, and 4 were characterized by IR spectroscopy, 1H and 31P NMR spectroscopy, and X-ray diffraction analysis. The reaction of complex 1 with enyne FcCH=CHC≡CFc gave rise to the Ru3(CO)6{μ3-P(Ph)CH2PPh2}{μ3-C(Fc)=CHCC(Fc)(1,2-C6H4)C(=0)} (6) and Ru3(μ-H)(CO)5{μ3-P(Ph)CH2PPh2}{μ3-C(Fc)=CHCC(Fc)(1,2-C6H4)C(—0)} (7) clusters. According to the spectral data, the latter compounds are isostructural to complexes 2 and 3, respectively.

Electrophilic hydrogen substitution reactions in η5-indenyl and η5-fluorenyltricarbonyl complexes of manganese and rhenium

Conclusions1.Upon acetylation or isotopic hydrogen exchange in acidic media, hydrogen substitution in η5-C9H7Mn(CO)3 occurs at both the 5-membered and 6-membered rings of the η5-indenyl ligand.2.Acetylation of η5-C9H7Re(CO)3 and η5-C13H9Mn(CO)3 occurs only at the six-membered ring of the η-ligand and is accompanied by cleavage of the metal-π-ligand bond.3.Competitive acetylation revealed that the η5indenyl complex η5-C9H7Mn(CO)3 is more reactive than the η5-cyclopentadienyl complex η5-C5H5Mn(CO)3 with respect to electrophilic hydrogen substitution reactions.

Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru2(CO)6−n(PPh3)n{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru2(CO)6{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh3 in refluxing toluene. The complexes were characterized by IR and by1H,13C, and31P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru3(CO)8(PPh3){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh3 ligand at the ruthenium atom of the ruthenacyclopentadiene moiety.

Hydrogenation of η5-fluorenyl ligand in the acetylation of η5-fluorenyltricarbonylmanganese

ConclusionsThe acetylation of η5-fluorenyltricarbonylmanganese is accompanied by the hydrogenation of the η5-fluorenyl ligand and formation of η5-(2-acetyl-3,4-dihydrofluorenyl)tricarbonylman-ganese, whose structure was established by x-ray diffraction structural analysis.