L. V. Rybin

σ,π-Binuclear complexes of transition metals coordinated to the monoolefin

Abstract σ-Vinyl derivatives of iron, tungsten, or rhenium react with iron nonacarbonyl to produce σ,π-binuclear complexes of the metals in which the presence of metal-metal bonds is very dependent on the nature of the metal. That the formation of the complexes containing a metal-metal bond does not necessarily involve the presence of an electron-withdrawing group attached to the vinyl ligand has been demonstrated for the σ-vinyl derivatives of iron, although it has been shown that for such bonding to be observed the double bond in the σ-derivative should be adjacent to the iron.

Acylation of iron carbonyl complexes of unsaturated aldehydes and ketones

Abstract The acylation of some iron carbonyl complexes of α, β-unsaturated aldehydes and ketones by (MeCO)+BF4− has been investigated and the structure of the salts obtained is discussed on the basis of IR and PMR spectra. Some chemical reactions of the cationic complexes have been studied and they were found to display high reactivity towards nucleophilic reagents.

Reactions and Synthesis, Wiley-Interscience, New York The reaction with amines of the adduct formed between (cinnamaldehyde)tetracarbonyliron π-complex and bf3. molecular structure of the formed σ-N-Tetra carbonyliron complexes of cinnamaldehyde imines

Abstract The adduct formed on reaction of boron trifluoride etherate with (π-PhCHCHCHO)Fe(CO) 4 by addition of BF 3 to the oxygen atom of the aldehyde group, reacts with primary amines to give σ- N -tetracarbonyliron derivatives of cinnamaldehyde imines via (enimonium)tetracarbonyliron π-complexes. The structure of the former complexes is established by X-ray analysis and the effect of steric factors on π → σ( N ) rearrangernent is discussed.

Unusual rearrangement of σ-vinylpalladium complexes into η2-olefin complexes. The structure of (η2-1-triphenylphosphonium-2-carbomethoxyethylene)(triphenylphosphine)iodopalladate

Abstract β-Substituted σ-vinylpalladium complexes [Pd(σ-CHCHCOOR)(PPh3)2(X)] (I) (X = Cl, I; R = Me, Et) have been obtained by interaction of the E- and Z-β-halogen acrylates with tetrakis(triphenylphosphine)palladium. On heating complexes I rearrange into isomeric η2-olefin-ylidepalladium complexes [ P dCH(COOR)-C HPPh3(PPh3)(X)] (II). The structure of these com X-ray study of the compound with X = I, R = Me.

Interaction of vinylgermanes with iron carbonyls. X-ray crystal structure of the Ge[Fe(CO)4]4 complex

Abstract The reaction between vinylgermanes and iron carbonyls yields, besides π-olefin complexes, the cluster compound Ge[Fe(CO) 4 ] 4 (I), characterized here by X-ray crystallography. The presence of an unsaturated substituent at the Ge atom plays an important role in the formation of I.

π-Allyl-σ-carbamoylcarbonyliron complexes from benzylideneacetone. Synthesis and π—σ rearrangement

Abstract Chelate π-allyl-σ-carbamoyl carbonyliron compounds (VIII) are formed in the reaction of the BF 3 adduct of (π-PhCHCHCOMe)Fe(CO) 4 with primary amines. The presence of a ring—chain tautomeric equilibrium of these compounds with the opened complexes (π-PhCHCHCMeNR′)Fe(CO) 4 (X) is confirmed by IR spectroscopy. In polar solvents the equilibrium is strongly displaced in the direction of chelate compounds VIII. In the case of the N -methyl derivative the ring-chain tautomerism is complicated by a previously unknown π → σ( N ) rearrangement with results in the formation of a tetracarbonyliron complex of benzylideneacetone N -methylimine with σ-coordination of the metal at the nitrogen atom. The mechanism of this rearrangement is discussed.

Chelate π-allyl-σ-carbamoyliron tricarbonyl complexes. preparation and molecular structure

Abstract The π-complex (chalcone)Fe(CO)4 with boron fluoride gives an adduct, which by action of primary amines yields chelate π-allyl-σ-carbamoyl complexes. Their structure has been established by X-ray analysis.

Reaction of iron carbonyls with pyridazine-3,6-diones The structure of (1,2-dimethyl-1,2-dihydropyridazine-3,6-dione) iron tricarbonyl

Abstract Reaction of 1,2-dimethyl- and 1-methyl-2-phenyl-1,2-dihydropyridazine-3,6-diones (I) with iron carbonyls gives iron tetracarbonyl complexes (II), which are converted to iron tricarbonyls (III). The π-olefin structure of II has been confirmed by IR and PMr spectra. X-ray analysis of (1,2-dimethyl-1,2-dihydropyridazine-3,6-dione)iron tricarbonyl (IIIa) showed that the iron atom is bonded to the heterodiene fragment of the cycle including two carbon atoms of the double bond, the ketonic carbon atom and one nitrogen atom.

Binuclear and tetranuclear complexes prepared by reactions of dodecacarbonyltriruthenium with the N-substituted cinnamic acid amides. Crystals and molecular structures of [Ru2(μ-H)(μ-η3-PhCCHC(O)N(CH2)4)(CO)6] and [Ru4(μ3-H)2(μ-η3-PhCCHC(O)N(CH2)4)2(CO)10]

Abstract The thermal reactions of Ru 3 (CO) 12 with the N-substituted cinnamic acid amides PhCHCHCONRR′ ( 1 ) in hydrocarbons yield the binuclear and tetranuclear complexes. [Ru 2 ( μ -H)( μ - η 3 -PhCCHC(O)NRR′)(CO) 6 ] ( 2 ) and [Ru 4 ( μ 3 -H) 2 ( μ - η 3 -PhCCHC(O)-NRR′)(CO) 10 ] ( 3 ), involving five-membered oxaruthenacycles η 3 coordinated by the second ruthenium atom. The structures of the complexes were determined by single-crystal X-ray diffraction studies. On heating in hydrocarbons, complexes 2 are converted into clusters 3 . The reverse transformation occurs on treatment of complexes 3 by methylene chloride.

Synthesis of 1,3-bis(dicarbonyl-η-cyclopentadienyliron)prop-2-en-1-one and its interaction with nonacarbonyldiiron. Crystal structure of octacarbonyl-(η-cyclopentadienyl)-μ3-ethylidyne-triangulo-triiron

Abstract Reaction of trans -β-chloroacryloyl chloride with FpNa (Fp = η-C 5 H 5 Fe(CO) 2 ) yielded the complex FpCHCHCOFp, which reacted with Fe 2 (CO) 9 to give trinuclear complexes IIa–IIc. The structure of IIc was established by an X-ray study.