SCIENTIFIC ABSTRACT KAZITSYNA, L.A. - KAZIYEV, T.I.

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• Collection: Scientific Abstracts
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• Document Creation Date: November 2, 2016
• Document Release Date: June 13, 2000
• Sequence Number: 9
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

TIAZAROT, I.N.; KAZITSYRA, ZAMSXAYA, I.I.
Determining the stracture of carbonyl compounds by
analyzing
a -dinitrophanylhydrazones of the same
'boorption speotra of 294
compounds, Yiz, sbor, no.3:185..187 157. (MMA ll:V-)
1. Nbskovskiy ordena Ionina i ordena Trudovogo
Irraenogo Znameni
goeadarstvenW universitet im. MA Lomonosova i
Inatitut orga-
nichaskoy khimii im. N.D. Zolinakogo AN SSSR.
(Stereochomistry) (Garbonyl compounda--apectra)

41z-
20-3-21/52
AUTHORSt Nesmeyanov, A. N. Academician, Ywitsyna L. A. , Lok3hin, B. V.
and Kritskaya, I. I.
TITLEs . . Position of Substituents in Ferrocene Compounds, as Determined
From Infrared Absorption Spectra (Opredeleniye polozheniya zame3ti-
teley v ferrotsenovykh soyedineniyakh po infrakrasnym spektram
pogloshcheniya)
PERIODICAM Doklady AN SSSR9 1957, Vol- 117, Nr 3, PP- 433 - 436 (USSR)
ABSTRACTs With respect to the possession of the apparently greatest series
of these spectra of ferrocene together with the derivatives, the
authors are able to draw the conclusion on the conformity of the
spectra mentioned, with some characteristics of their structure.
These conclusions helped at the establishment of the structure of
the ferrocene homologues, and rendered possible the precising of
structure of the condensation products of the formaldehyde and
other aldehydee with ferrocene. Up to ncw the first author has
worked out together with E. 0. Perevalova (reference 17) two moth-
ode of the determining mentioned in the title, both of which ahow
limitations. 1.) Catalytic hydrogenation under rigorous conditions
Card 1/4 leads to corresponding cyclopentano derivatives, 2.) Bromination

R.
20-2.2V52
Position of Substituento in Ferrocone Compounds, a3 DeLi-.iined From Infra-
red Absorption Spectra
ASSOCIATIONt Institute for Zlemen'c-ul-organic Coripuunds All USSR
(Institut elementooc__i-*!,-:iouki1:h joyedineriiy Akaderiii natik SSSR)
SUBMITTEDt June 26, 1957
AVAILABLE: Library of Congress
Card 4/4
5 (3,4)
AUTHORS: Kazitsyna kshin, B. V., SOY/55-58-6-26/31
o, L. L., Terentlyev, A. P.
TITLE: Infrared Spectra of Several Inner-~complex Compounds in the
Field of the Valency oscillations of N-H (Infrakraswe
spektry askotorykh vnutrikomplekanykh soyedineniy v oblaoti
valontnykh kolebaniy N-H)
PERIODICAL: Vestnik Moskovskogo univere iteta. Seriya matematiki
mekharLiki,
aetronomii, fizikil khimii, 1958,13Nr 6, pp 207 - 21; (USSR)
A
ABSTRACT: The object of this article is the investigation of the struc-
ture of the inner-complex compounds of the quadri--coordinated
metals (Cu, Ni, Pd, Be, Zn, Cd) in which a successive modifi-
cation of the electronic shell takes place. These metals are
capable of forming tetraedric or even (in this case cis- and
tranBisomere) complexes. The examination was carried out by
means of infrared-absorption spectra. These spectra permit a
determination concerning the existence of the transisomerat
as with the latter the symmetrical oscillations are not ac-
tive in the infrared spectrum owing to the absence of a change
of the bipolar noment. In order to draw conclusions as to the
Card 1/3 even cis-shape or the tetraedric shapaq further toots are re-

Infrared Spectra of Several Inner-complex Compounds
BOY/55-58-6-26/3i
in the Field of the Valency Oscillations of N-H
quired. In the present paper the authors restricted their in-
vestigations to the possibility of determining the even trans-
-configuration. Infrared spectra were taken of a number of
com-
pounds containing the atomic group of HN-Me-NH. The authors
tried to find out the configuration, taking into account the
absorption bands in the field of the valency oscillations of
the N-H bond. The following compounds were investigated:
Cu,Ni,
Fd#CdpBe, iminatee of salicyl aldehydep the seetyl-aoetone
imi-
nates of Cu, Ni, Pd, the o-oxyacetophenone iminaten of Cu and
Ni, the P-oxynaphtaldehyde-iminates of Cu and Ni and the cop-
per salts of the ethylene-bia-a-iminopropions- and of the a-
phenyl acetic aoid. The experimental part contains a short de-
scription of the syntheses of the various complex oompoundal
the outward form and the contents of nitrogen and copper are
shown in table 1. In figure I the spectra of those compounds
are shown whose X-ray structural analyeds and magnetic me&-
suremente seemed to point to a trans-structure. Figure 2 rei-
fers to the spectra of the Cd and Be salicylal iminates which
are of tetraedric structure, and to the spectra of the last-
Card 2/3 -mentioned compounds, which - owing to the prestnee
of an

Infrared Spectra of Several Inner-complox Compounds
BOV/55-58-6-26/31
in the Field of the Valency-Oneillations of--N-H -
othylone-bridge - show an even Cis-configuration. Table 2 in
a
oompilatibn of all results, ofiaracteriving the absorption of
the compounds investigated in the field of the
N-H-binding'va-
loncy-oncillatione-. The data obtained permit the following
con-
clunions to be drawn: the composite bapdo of the dis- and
trans-
-configuration are generated under the influence of the
crystal
lattice. If in the-field of the valiency oscillations but one
band bsoomes.clearly visible, this in considered an a-proof
that there is au'even- trans:-configu'ratio~L. If in
solutions this
one band romaine unchanged in spite of another-lecisaion,
then
t~e existence of this band is only a proof for an
evan'trans'.
-figuration, if the solvent doei not exercise any Influence
on
the interaction between the metal-atom and the donor atoms.
There are 2 figures, 2 tables, and 8 references, 2 of which
are
Soviet.
ASSOCIATION: Kafedra organicheskoy khimii (Chair for Organic
Chemistry)
SUBMITTED: July 25, 1958
Card 3/3

24(*7),7(3)
SOV148-23-10-10139
AUTI,.'ORS:
Kazit .,LokElhin, B.
V., Polstyanko, L. L., Terent 'yov, A.P.
TITLE:
The Infrared
Spectra of Some Innercomplex Compounds Within the

Range of
NE-Valence Oscillations
PE'RIODICAL:
Izvestiya Akademii nauk
SSSR. Seriya fizicheskaya, 1959, Vol 23,

Nr 10, pp 1196-1198
(USSR)
ABSTRACT:
The authors investigated a number of
irinercomplex metal compounds

(coordinate number 4) by means of
infrared spectra within the

range 3000 - 3500 cm- 1 and
determined the NH-valence oscillation

NH and NH NH
frequency in the formations 0

\

Me Id,

\
\

0 0
0
11N

The formulas for the structure of the investigated
compounds are

given (Me denotes the metal). The substance to be
investi.-ated

was prepared as vaseline paste; measurements were
carried out by

using a spectrophotometer of the type IKS-11.
The results are

shown by a table. Figures 1 - 3 show the
characteristic shape of
Card 1/2
the spectra of three compounds.
The data given by the table are

The Infrared Spectra of Some Innercomplex Compounds
SOV/48-23-10-10/39
Within the Range of NH-Valence Oscillations
I
then discussed. One or several bands may occur in the spectrum.
If one band occurs in the spectrum of an innercomplex compound
containing an Iffi-group in connection with NH-valence
oscillations,
this may be considered to prove the existence of a plane trans-
structure of the complex. The non-existence of a splitting-up
in the spectra of solutions and the occurrence of only one band
may be considered to prove the existence of a trans-structure
only if the solvent exercises no essential influence upon the
interaction between the metal and the donor atoms. There are
3 figures, 1 table, and 4 references, 1 of which is Soviet.
Card 2/2

50A)
.1.
AUTHORS:
Kazitsyna, Le As, Polstyanko, L. L.,
SOV/20-125-4-32/74

~pef`ska7a,_N._B., Ignatovich, T. ff.,
Terentlyev, A.P.,

Corresponding Member AS'USSR
TITLE:
Investigation of the Absorption Spectra of the Alkylimines

of
o-Oxycarbonyl Compounds (Issledovaniye spektrov

pogloshcheniya
alkiliminov o-oksikarbonillnykh soyedineniy)
PERIODICAL:
Doklady
Akademii nauk SSSR, 1959, Vol 125, Ur 4, PP P07-810

(USSR)
ABSTRACTt
For the purpose of determining the type of bond
between metal

and the donor atoms in the inner-complex
compounds the

comparison of the spectra of the initial addenda
and the formed

inner-oomplex compounds is used. The maintenance
of the spectral

character of the addendum in an inner-complex
compound gives

evidence of a formation of an "ionic" bond: a
d6cisive change

of the type of spectrum in the produced
complex, however points

out to the formation of a covalent bond
between metal and donor

atoms (Ref 1). In the former case it is
possible to determine

the strength of the forming Izond (Ref 2)
by the degree of shift

of the bands of the inner-complex
compound. The authors
Card 1/4
investigated the spectra of
inner-complex compnunde of addenda

Investigation of the Absorption Spectra of the 301/20-125-4-32/74
Alkylimines of o-Oxycarbonyl Compounds
as a0etyl acetone, salicylaldehyde, o-oxyacetophenone,
A-oxynaphthaldehyde and their alkylimines (Ref 3). All
mentioned compounds form hydrogen bonds of different type and
strength. In order to determine the initially mentioned changes
in the spectrum which are due to the formation of a hydrogen
bond, the electron spectra were investigated in different
solvents. It was found that in addenda containing only hydrogen
as donor atoms the hydrogen bond does not cause a remarkable
variation of the spectrum character: only some main bonds are
shifted in the direction of the long waves. However, in addenda
as alkylimines of salicylaldehyde and o-oxyacetophecone a new
bond appears within the range of 25000'em- 1. Its occurrence
and intensity are determined by the used solvents. In inert
solvents (isooctane, carbon totrachloride) the spectm of
alkylimines are similar to those of oxygen compounds not only
with respect to their character but also with respect to the
position of the abuorption bondso In this case the hydrogen
bond appears also as a shift of the main bands by 1500-2000 cm
Card 2/4 in the red direction (Table 1). There is a great
difference

lr7estigation of the Absorption Spectra of the JOY/20-125-4-32/74
Al,ylimines of o-Oxycarbonyl Compounds
between the spectio. of the two last Mentioned alkyli.mines in
polar solvents and those in inert solvents, and thus there is
also a considerable difference between them and the spectra of.
oxygen compounds. The above investigation shows that a direct
comparison of the spectm of such addenda as alkylimines of
salicylaldehyde and o-oxyacetophenone with the spectra of the
inner-complem compounds produced from them is permissible if
spectra in polar solvents are concerned-As the inner-complex
compounds of these two substances are as a rule not soluble
in inert solvents and as it is necessary to take their spectra
in chloroform and alcohol for the purpose of determining the
form of bond it is advisable to iake use of the comparison
between alkyltmines and spectra in not polar substances. In
the case of "ionic" compounds it is of advantage to determine
in not polar solvents the relative strength as a function of
the spectrum of the methyl ester of the addendum concerned,
i. e. as a function of ouch a opectrum that is not changed
under the action of inner- or intramolecular interactions.
There are 3 figures, 2 tables, and 5 references, 1(2) of which
Card 3/4 are Soviet.

50).
AUTHORSs Neameyanovp A# Nt, Academician, SOV/20-125-5-23/61
Kazitsyna, L. A., Lokshin, B. V., Villchevskaya, Y. D.
TITLEs Infrared Spectra of Some Alkyl- and Arylferrocenes
(Infrakrasay,ye spektry nekotorykh alkil- i arilforrotoonov)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 125, Nr 5,,
PP 1037-1040 (USSR)
ABSTRACT: It was proved earlier that frequencies within the
range of
1000 and 1100 cm- 1 in the infrared spectrum of ferrocene
derivatives may be indicative of the presence of a
cyclopentadienyl ring free from subetituents (Refs 1, 2).
The next problem to be solved is the determination of the
mutual position of the substituting groups in a ring of
the homoannular disubstituted ferrocene derivatives. The
authors succeeded in obtaining 1.2.- and 1.3-isomers
according to these spectra for acetylethyl- and
ethyl-dimethyl
ferrocene. However, the attempts which were made to use the
derived rules for other homoannular disubstituted ferrocenes
Card 1/3 failed. The authors investigated the infrared
spectra of

Infrared Spectra of Some Alkyl- and Arylferrocenes
SOV/20-125-5-23/61
some substituted ferrocenes within the range of the
NaCl-priem (Table 1). It was reported (Ref 1) that the
20
spectra of two diethyl-ferrocenea (n. 1.5820 and 1.5847)
differ only by the frequency 1277 cm-1, which is observed
in one spectrum only. Since either spectrum exhibits
absorption within the range of 1000 and 1100 cm- I (which
indicates a free cyclopentadienyl ring), their structure
has to be either 1.2- or 1-3-diethyl-ferrocene. Absorption
within the range of 1280 cm- 1 is observed in all
monosubstituted alkyl-ferrocenes (except methyl-ferrocene),
phenyl-ferrocene, and all alkyl- and aryl-ferrocenes
dieubstituted in various rings, and, finally, in homoannular
di-isopropyl and di-tert-butyl-farrocenes. In the case of the
last-mentioned substances a 1.3-structure is more probable,
due to sterio considerations. However, absorption within
the range of 1280 cm- I is lacking in constantly
1.2-substituted
homoannular ferrocenes (substances Nr 11 - 13, Table 1), in
Card 2/3 which a 1.2-poBition of the aub8tituents results
from their

Inf-rared Spectra of Some Alkyl- and Arylferrocenes
SOV/20-125-5-23/61
bicyclic structure. The synthesis of the compounds 11 and
12 was given earlier (Ref 9). The synthesis of Nr 13 is
described in the present paper. The data discussed here
render the assumption probable that the absorption within
the range of 1280 cm- I is owing to the presence of two
carbon
atoms of ferrocene. These atoms are not substituted and
adjacent to a carbon atom of ferrocene to which a hydrocarbon
radical is bound. The occurrence of these bands in the
spectra of homoannular diBubstituted ferrocenes indicates
the 1-3-Position of the substituents. There are 1 table and
12 references, 8of which are Soviet.
ASSOCIATION: In8titut elementoorganicheskikh soyedineniy
Akademii nauk SSSR
(Institute of Elemental-organic Compounds of the Academy of
Sciences,USSR)
SUBMITTED: January 30, 1959
Card 3/3

5 (2)
AUTHORS: Nesmeyanov, A. X., Academician, SOV/20-127-1-30/65
-Kazitsyna, L. A.t Lutsenko, I. F.,
Rud
TITLE: A Spectroscopic Investigation of a-Metalated Aldehydes-
and Ketones and Lithium Vinylate (Spektroskopicheakoye issle-
dovani e a-metallirovannykh alldegidov i ketonov i vinilata
litiya~
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 127, Nr 1, PP 115 - 116
(USSR)
ABSTRACT: The a-mercurized aldehydes and ketones are able to react in two
ways (at C and 0) and to form two series of derivatives (Refs
1-3). Either compounds are formed by the direct substitution of
an Hg-atom (reaction with triphenyl-chlo-.o-methane , or (as
e.g. in the case of the reaction with acid halidee~ the reac-
tion center shifts in consequence of a distinctly marked con-
jugation of the Hg-C and C-0 bonds (d - n - conjugation).
The above-mentioned conjugation is distinctly marked in the
substances mentioned in the title due to the presence of a me-
tal atom with comparatively high polarizability (Hg~ Sn).
Card 1/3 Changes in the absorption bands of the carbonyl group of these

A Spectroscopic Investigation of a-Meta'Lrtted SOV/20-1 27-1
-30/65
Aldehydes and Ketones and Lithium Vinylate
compounds in the oscillation- and electron spectra can there-
fore be expected. The authors investiCated the ultraviolet- and
infrared spectra of eight mercurized carbonyl compounds and of
two ketones which contain Sn-atoms in a-position to the C-0
group. Table 1 shows that the frequencies of the carbonyl group
in the infrared spectrum are in fact considerably shifted under
the influence of the Hg-atom (Ref 4). Table 2 shows the absorp-
tion maxima of the same compounds in the ultraviolet light,
furthermore, those of acetaldehyde, isobutyric aldehyde, and
acetone for comparison. An intenseabsorption band within the
range (280-300 mg) occurred in these spectra of the Hg- and
Sn-derivatives of the oxo-compoundag which is characteristic
of carbonyl compounds; intensity increased by 200-300 times.
The above-mentioned data confirms again the existence of an
6-n-conjunction in the compounds mentioned as can be proved as
well by several chemical reactions. Furthermore, the ultravio-
let- and infrared spectra of a very simple metal enolate were
investigated, the structure of which is isomeric to that of
Card 2/3 RCOCH2Me (1). Lithium vinylate (Ref 6) was
inveutigated. Ab-

A Spectroscopic Investigation of a-Met-p-lated dov/20-1 27-1
-30/65
Aldehydes and Ketones and Lithium Vinylate
sorption bands of the carbonyl group lacked here completely.
A moderately intense band which corresponded to the C-C double
bond was, however, found to occur in the infrared spectrum at
1
1610 cm- . It was considerably shifted due to metal influence,
which is well in line with the shifting of the double bond
con-
Jugated with a phenyl- or carbonyl group (Ref 4). This
confirms
earlier conclusions concerning the C-structure of the organo-
mercury compounds obtained by the addition of Hg acetate to
ether and ester as well as concerning the O-structure of the
cleavage product of mercury-bis-acetaldehyde by alkali metals.
There are 2 tables and 6 Soviet references.
ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V.
Lomonosova
(Moscow State University imeni M. V. Lomonosov)
SUBMITTED: April 20, 1959
Card 3/3

5 (3)
AUTHORS: Kazitsyna, L., A., Lokshin, R. V., SOV/20-127-2-27/70
TITLE: The Infrared Spectra of Ferrocenes. On the Reciprocal
Influence
of Substituents in the Perrocene 4"'olecule
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 127, Nr 2~
PP 333-336 (USSR)
ABSTRACT: Recently it was proved that the reciprocal influence
of the
substituents is passed on through the entire ferrocene system
from ring to ring (Refs 1-3). The authors dre,.-, this
conclusion
on the strength of the comparison of the dissociation constants
of the ferrocene-carboxylic acids of the Vpe Y-C 5H4-Fe-C5H4-
COOR.
The substituents form with respect to their effect the
following
series: C4H 9< C2H5< H< COOCE 3< COCH3< MIT < so2NH 2< so2F.
The
substituents on the right side of the hydrogen increase the
dissociation constant of hydroxyl, whereas the left ones reduce
the latter. The reciprocal influence of the substituents can be
expressed in the ferrocene system by the frequency change of a
substituent in one ring under the influence of different
subati-
tuents in the second ring of the molecule. Since the
frequencies
Card 1/4 of the carboxyl group are very characteristic the
authors could

The Infrared Spectra of Perrocenes. On the Reciprocal
SOV/20-127-2-27/70
Influence of Substituents in the Perrocene Molecule
carry out spectroscopic investigations for the above-mentioned
series in the infrared range also for ferrocene carboxylic
acids
which have unequal substituents in the other cyclopentadienyl
ring. Table 1 shows the obtained spectra. The infrared spectra
were absorbed by the solution in order to eliminate additional
effects caused by intermolecular interaction. The authors were
forced to use chloroform because of the low solubility of most
of the compounds investigated, in spite of the favorable
properties
of tetrachloromethane. Table 2 shows the oscillation
frequencies
of the C-0 group in solutions and in solid state. They show
the
change of the frequency of the carbonyl group in the
transition
from solid state to solution. The division of the
frequericiec in
solid state is neutralized in the solution, although one of
the
carboxyl bands is apparently blurred. This phenomenon is
assumed
to be caused by an interaction with the solvent. The
comparison
of the frequencies of the C-0 group shows that the frequency
of
the carbonyl group ic considerably changed under the
influence of
the substituents in the second ring. -r)irthermore it follows
from
table 2 that the increase of the electrophilic property of the
Card 2/4 subatituents increases the fronuency of the C-0 bond
of carboxyl

The Infrared Spectra of Ferrocenes. On the Reciprocal
SOV/20-127-2-27/70
Influence of Substituenta in the Ferrocene Molecule
(and of carbomethoxyl) which is located in the other ring of
the
ferrocene molecule. The substituents are on the strength of
this
placed in two different series with respect to the influence
on
carboxyl and on carbomethoxyl. These series agree well with
each
other and with the series initially mentioned in the
abstract.
An exception is the position of the absorption bands of the
not
substituted acids and eaters (1682- 11 1712 cm- 1
respectively),
i.e. the hydrogen is located in the series between the groups
CH3CO and CH 3OOC, whereas in the initially mentioned series
it
was located between the alkyls and the COOCE, group. This
could
not be explained for the time being. The influence of the
sub-
stituents is passed on from ring to ring in spite of this
divergence. There are 2 tables and 3 Soviet references.
A53001ATIONs Moakovskiy gosudarstvemiyy universitet im. IT.
V. Lomonosova
(Moscow State University imeni M. V. Lomonosov)
Card 3/4
D-zz

5.3700 78300
SOV/79-30-3-54/6~f
AUTHOU: Kazitsyna, L. A., Reutov, 0. A., Buchkovskiy, Z. F.
TITLE: Double Diazonium Salts of Thallium
PERIODICAL: Zhurnal obstichey khImii, 1960, Vol 30, Nr 3,
pp 1008-1012 (USSR)
ABSTRACT: A series of double sa!tB of' diazonlum thalliurn
chlorides,
(ArN2C')2t'C'3,f were prepared and their absorption
spectra taken. It was found that Linder certain condi-
tions interconversion of 1!1 and 2:1 double salts takes
place:
2r-X