L. I. Leont'eva

Reaction of organonickel σ complexes with p-tolyl isocyanide

p-Tolyl isocyanide reacts with the cymantrenyl, phenyl, and mesityl complexes of nickel to give the products of inserting the isocyanide at the Ni-C σ bond and the simultaneous displacement of the triphenyl-phosphine ligand.

Reaction of π-cyclopentadienyl-(σ-ferrocenoylmethyl) iron dicarbonyl with electrophilic reagents

1. π-Cyclopentadienyl-(σ-ferrocenoylmethyl)iron dicarbonyl reacts with HgBr2 or CH3-COC1 with a cleavage of the Fe-C σ-bond. 2. Carboxonium salts are formed when π-cyclopentadienyl-(σ-ferrocenoylmethyl)iron dicarbonyl is reacted with mineral acids. 3. HC1 and I2 easily cleave the Hg-C bond in bromomercuriacetylferrocene.

Pi-allyl complexes of iron and tungsten cyclopentadienylcarbonyl

ConclusionsPhotochemical and thermal decarbonylation of the σ-allyl complexes affords π-2-ferrocenyl-3,3-dicyanoallyl complexes of the dicyclopentadienylcarbonyls of iron and tungsten.

Photochemical reactions of organotungsten compounds of cymantrene series with triphenylphosphine

Conclusions1.The tungsten σ-(π-cyclopentadienyl)manganesedicarbonyltriphenylphosphine complexes (CO)2(PPh3)MnC5H4W(CO)3Cp and (CO)2(PPh3)MnC5H4,COW(CO)3Cp were obtained.2.The photochemical reactions of (CO)2(PPh3)MnC5H4W(CO)3Cp and (CO)2(PPh3)MnC5H4COW(CO)3Cp with PPh3 gave the products of replacing the CO group on the tungsten atom by PPh3, and respectively (CO)2(PPh3)MnC5H4W(CO)2(PPh3)Cp and (CO)2(PPh3)MnC5H4,COW(CO)2 (PPh3)Cp.

Mercuration of σ-cymantrenyl-(π-cyclopentadienyl)dicarbonyliron

We were able to mercurateσ-cymantrenyl-(σ-cyclopentadienyl)dicarbonyliron in the cyclopentadienyl ring of the cymantrenyl group to give C5H5(CO)2FeC5H3(HgCl)Mn(CO)3 and [C5H5(CO)2FeC5H3Mn(CO)3]2Hg.

Reactions of the ketone group in σ-ferrocenoyl methyl(π-cyclopentadienyl)dicarbonyliron

1. Reaction of σ-ferrocenoylmethyl-(π)-cyclopentadienyl)dicarbonyliron with HBF4 and triethyloxonium fluoroborate gives carboxonium salts of the type [C5H5(CO)2FeCH2C(OR)C5H4FeC5H5]+BF4−, where R=H and C2H5, and reaction with iodine in ether gives a ketone-group complex with iodine. 2. The reactions of the ethoxycarbonium salt [C5H5(CO)2FeCH2C(OC2H5)C5H4FeC5H5]+BF4−-with Nal, NaOCOCF3, and PPh3 proceed with cleavage of the Fe-Cσ bond, while its reaction with NaBH4 proceeds without cleavage of this bond, while its reaction with NaBH4 proceeds without cleavage of this bond but with formation of C5H5(CO)2FeCH2CH(OC2H5)C5H4FeC5H5.

(2-Ferrocenylethyl) (π-cyclopentadienyl) dicarbonyliron

We have prepared (2-ferrocenylethyl) (π-cyclopentadienyl) dicarbonyl iron by reaction ofπ-C5H5(CO)2FeNa with 2-ferrocenylethyl p-toluenesulfonate or 2-ferrocenylethyl chloride. We have examined its reactions with triphenylcarbonium tetrafluoroborate, ferricinium tetrafluoroborate, mercury(II) chloride, iodine and triphenylphosphine.

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

The photochemical reactions of (CO)2(PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3 gave the products of replacing the CO on the Fe atom by PPh3: respectively (CO)2(PPh3)MnC5H4Fe (CO)(PPh3)C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)(PPh3)C5H5.

π-Cyclopentadienyl(σ-ferrocenoylmethyl)dicarbonyliron

1. The reaction of chloroacetylferrocene with C5H5Fe(CO)2Na gave π-cyclopentadienyl(σ-ferrocenoyl-methyl) dicarbonyliron. 2. The σ-bond in π-cyclopentadienyl(σ-ferrocenoylmethyl)dicarbonyliron is cleaved under the influence of iodine, C5H5Fe(CO)2Na, LiAlH4, phenyllithium, and π-cyclopentadienylmanganesetricarbonyllithium. 3. π-Cyclopentadienyl-σ-(π-cyclopentadienylmanganesetricarbonyl)dicarbonyliron was obtained.

Reaction of salts of triferrocenylmethyl cation with nucleophilic reagents

Salts of the triferrocenylmethyl cation react with methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium chloride, tert-butylmagnesium chloride, n-butyllithium or sodium ethylate to give the corresponding derivatives of the triferrocenylmethane series.