V. A. Dubovitskii

Study of the transfer of electronic effects of ligands in mono- and biscyclopentadienyl derivatives of titanium in various solvents

1. Employing the19F NMR method it was found that the effect of cyclopentadienyls (CPD), containing various donor substituents, is transmitted to the fluorine atom that is found in the p-position of a phenyl group that is present in the mono- and bis-CPD-aroxy derivatives of titanium, and also to the fluorine atoms in the trifluoroacyl derivatives of titanium. 2. In the case of the mono-CPD derivatives of titanium the ability to transmit the electronic effect depends on the complexing properties of the solvent (the effect of various CPD on the fluorine atom in the ligand is not transmitted in solvating solvents); in the case of the bis-CPD derivatives this dependence is absent for all of the investigated solvents. 3. A study was made of the ability of a number of oxygen-, nitrogen-, and sulfur-containing solvents to undergo coordination with the titanium atom in CPD-tri-(p-fluorophenoxy)titane.

Mono(cyclopentadienyl)alkoxytitanium halides

1. Mono(cyclopentadienyl)alkoxytitanium halides were synthesized by reverse disproportionation reactions. 2. The preparation of pentamethylcyclopentadienylethoxytitanium chlorides is described, along with the synthesis of pentamethylcyclopentadienyl(cyclopentadienyl)titanium dichloride. The latter compound is the first bis(cyclopentadienyl) derivative of titanium known to contain a completely substituted cyclopentadienyl ring. 3. The IR spectra of the compounds were studied.

Some data on the character of the titanium -cyclopentadienyl ring bond in C5H5Ti(OC2H5)3 and (C5H5)2 Ti(OCOCH3)2

On the basis of the formation of ferrocene during the reaction of C5H5Ti(OC2H5)3 and (C5H5)2Ti(OCOCH3)2 with FeCl2 and the ease with which the bond of the cyclopentadienyl ring with the metal in these compounds may be hydrolyzed the hypothesis has been stated that the bond of the titanium atom with the cyclopentadienyl rings in (C5H5)2Ti(OCOCH52 and C5H5Ti(OC2H5)3 has an ionic character to a considerable degree.

Synthesis of aroxy derivatives of cyclopentadienyl- and bis(cyclopentadienyl)titanium and fluoroacylates of mono- and bis(cyclopentadienyl) titanium

1. A method was developed for the synthesis of cyclopentadienyl(CPD)-triaroxytitanes by the reaction of CPD-triethoxytitane with aryl acetates. 2. Various CPD-triaroxytitanes were obtained for the first time, and a study was made of their chemical properties and IR spectra. A number of fluorophenoxy derivatives of mono- and bis-CPD-titane, containing various cyclopentadienyl radicals, was obtained, as well as the trifluoroacetates of the mono-and bis-CPD derivatives of titanium. 3. In the alcoholysis of the CPD-triaroxytitanes the lability of the CPD ring changes as a function of the character of the substituent that is found in the aroxy group.

Reaction opposite to disproportionation and transesterification in the series of monocyclopentadienyl derivatives of titanium

1. A method was developed for producing monocyclopentadienyl derivatives of titanium, containing various groups of atoms at the metal atom, based on the reaction opposite to disproportionation. 2. The possibility of conducting the transesterification of cyclopentadienyltrialkoxytitanium with complex esters was demonstrated. 3. Previously unknown methyl- and ethylcyclopentadienyl derivatives of titanium and certain dialkoxy derivatives bis-cyclopentadienyltitanium were described.

Infrared spectra of certain mono- and bis- cyclopentadienyltitanium diacylates

1. In an investigation of the IR spectra of a number of mono- and bis-cyclopentadienyltitanium acylates, monodentate coordination of the acyl ligand in these compounds was established. 2. For cyclopentadienyltitanium triacetate, an intermolecular interaction on account of the formation of bridge bonds, accomplished by part of the acetoxy groups of the molecule, was detected.

Synthesis of dialkoxy(or aryloxy)titaniu'm oxides by the transesterification of dipropoxytitanium oxide

1. It was shown that dialkoxy(or aryloxy)titanium oxides and bistriethylsiloxytitanium oxide can be prepared by the transesterification of the readily accessible dipropoxytitanium oxide. By this method we synthesized (C2H5O)2 TiO, and (i-C5H11O)2TiO, (n-C6H13O)2TiO. (C6H5O2TiO, [(C2H5)SiO]TiO. 2. In dilute benzene solution titanium oxide bisacetylacetonate is a monomeric substance.

Change with time of the degree of association of alkoxytitanium compounds in benzene solution

1. The degree of association of alkoxytitaniums of the type\((RO)_4 Ti; CITi(OR)_3 ; (RO)_2 TiO; \begin{array}{*{20}c} {Cl \setminus } \\ {RO / } \\ \end{array} TiO; \begin{array}{*{20}c} {Cl \setminus } \\ {RO / } \\ \end{array} TiO \cdot ROH; Cl_2 TiO \cdot \) ·2ROH in benzene solution decreases with time. 2. As cryoscopic determination showed, substances of this type behave as monomers after a few hours. This makes it possible to use cryoscopy for determining the molecular weights of alkoxytitaniums in their monomolecular form.