SCIENTIFIC ABSTRACT FR:BEREZIN, B.P. TO:BEREZIN, B.D.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000204800017-6
• Release Decision: RIP
• Original Classification: U
• Document Page Count: 3
• Document Creation Date: November 2, 2016
• Sequence Number: 17
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTR

APPROVED FOR RELEASE. 06/23/11 CIA-RDP86-005138000204800017-6

APPROVED FOR RELEASE. 06/23/11 CIA-RDP86-005138000204800017-6

APPROVED FOR RELEASE. 06/23/11 CIA-RDP86-005138000204800017-6

APPROVED FOR RELEASE. 06/23/11 CIA-RDP86-005138000204800017-6

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~,
-
_ACCESSION NR: aP~o3457:i -- -- - -- --- -~ - - -- -- -- - _ _._ ,
---- - _ ..
' L' + f
nature of the central afi~am. The dieaociatian of metalphthalocyanines (Nl~c ~
' i aqueous proton�containin,g solutions is irreversible. MPcH` t 2Fi O _....,. 2~
' Mai -~' I
HgPcH ~ The entropy at~d, energy of activation off' this diesaeiat~.on reaction wex~ I
r ; cal.cu~t'~ed.. ~t wraa su asteci that in tbs process old tha trimo~.scu,la~c
f I:activvr~ted c~tplex (MPc~'~~H~p+~* forma fx~ tha initial. t . ~actian the
;their strong mutual la:rization. D4'eH and H~{} because of !
~ Po The negative values of the entz~rpy aP activation
~; ~ ~ are axp~ by the high charge acad. atxo
which makes it more stzbr ~ Po~,~ation of the activated complex
f 'solvated than the initial. particles. The special role`
~ : ~ of the H 0 t as a source ~;>fl Hip molecules required for the formation of the f
i , i tad camp~ex t~ud, clsti~;-n oi' the dissoc~.ation is ,~ activa�
i :took part in the exper~,m~~ln work. "... " pointed cut. N9 ~. Sosn~.k~Va i
~ j' cuaaion of the given ~roxl;." Ox~.g. art. h$a s~~ prof. K. A. Yats~mir,~k for dis� i
! .~, ~ 3 tables, ~ figurr~.a aadt 7 equations.
~ ~ssOC~:Ax~xo~r: xvanovslciy ~o�'~lagxches~.y institut ~,
{ nolagical. ~atitute} ( ova C#,c~, Tech- 1
' ~' i
.,
~'' SUB COBBs ~ ~ -
.... MO ~' s~}"H't Old 0~
~5
~, ..
Cc~r~ ? ~~~ ~ ~ ~ t
~,~..~ _.._... _ ., _.... ~_wr.. -~..........,_.,~., .~._. __~ _~._..._ .....M ...._~.~x _ ., . ~m..,. .~ .~~. -- - _~,__ . _.......w,.._,, .......~._.....,,~. _.._._... . , r ,.,...w. - ,
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L
1 .-. n~w:i.Y. -r4.~t:.::fiw~i!
i
~. wi-41.1M,a. _.a

~..__.,.-'_"a.~ r.u.~~+.w.a-neswnR.m.N.sew~..s.-�.Ml~f~w .Je~w'M~i~wacw+�. ' r.. ~..+..F..av,.~ t.. ._r. rwn~.ue~~wr.~aw, tsusww MA.. _ _

ACC~S5IC~1 NR: AP~0,31~57.~
AC~i'IiOR: , Berezin, ~� D� (Tv~uao~m) .
TITLE: The meeban~.sm a:E` di$saciation ~of raetalphthalacyanines
sorr~c~: Zhurnal Yizichl~$ko~ khimii, v. ~8, urn. 4, 194, 8~ar$y~'
I � TO~C TAGS: metat th-s1: c
pb yanin$, dissaaiation, mechanisms di.aeociatioa rate,
aCtivatiou @t71@,*.'~t', aCti''i~at~,Qri erttx~py, metc~Ilphtloalocymnin@ ~iYdxnnium ion Compl@~,~
tl'~01@CUlax` 1"@BCtion r
A&STRACTt The dia$oaia~i~~.an rate of stable Ca, Ni, Al, Ge, OSEI'V~,, Rh{~22~phthal>a-
~ cyanine;a ixt gulriaric ac,lld solutiane in the 140.160G range xas :Lnvesti~ated,. The
(;general equation
I dCMpol;+
' dt �' k~apQ~i+~~ia+.
~trh>axe a~cg+ is the co2;~c@ntration oY th� phtbalocyamfne proton is solution} ~
'- ~ Pound to obtain Por the diseo~.ation oP tY~ metalpb es ragerd~.ess of the
l~ ~ }
i:.....,~.._.,
Card 1.--1j"~2...._-Y.._ ..__._~.w_......~..q..~....,....,~~,..,. .. _.~....,..~......Y..._....,._..~....._.__......_._.__.._........_..._...wr_~--~1_.___..~.. ..
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~~
,~

~ i'' 1
,
"".'" s ~_ ___.... .~_.' ....
ACCES510N NR; AP1~0416~0
remaining bands are caused by'~1~~''l'r~ti transitions. In a series of
divalent cations the short wavE shift increases in propartian to
the stabi~.ity of the complex; the shift with tri- and tetravalent
cations is still greeter. However the magnitude o#' the hypsochrvrn~.c
shift does not correspond to the stabil~.ty of the complex. Thus
it was shown the shy. ~'t; of tha primary absarptian band of the electron
spectra of the Tr ~lig~:~nds der~ends riot on~,y on the strength of the s-~
band but appears t-a 'tie alsa a function of the nature and strength
o.i the ~-band, of th~a magnitude of the ~:#'fective charge of the cen-
tral 3.an in the complex, and a~' the geometric factor of the distort-
ion of the ligand of the gym-system upon caordinati.on. All of these
electronic and structural factors have a d~.ffcrent effect on the
strength of the eomp;Lex and on the e.l,ectronic equilibri~~n~ of the !~
1.igand. It is there.:Pore indicated tli:tt the spectral criterion used
in foreign works { i..~~a . , the greater strength a.f the campJ.exes with
organic lrwligands re~~ul,ts in the greater hypsochromic shifty has
very limited valued Tha energy eclui.libria of the co~~plex, cation
and cyclic '~-ligand ,ire spawn schematically ~.n ~+'iga ~ Q Ari.g~ arte
has: ~ tables and 5 ,;"igures&
Card 2~~1, .... ~ ... -
.. ~ .> ..., _ .A n. .. a ..t .. .a ._. i.. y,y .~., _.~,
_. _. _ _ ~_ ~_____-.i__.__..._..._. .. \ -.i.
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w4!irio~�wr~w.J~.+..4 ~ti}aM'iwf'~l..f.~l~:f.. iii ... ~ '. _ _- a~..,.r. ~ K
- ,�~.~'
t .. _
� #
i
. '
ACCESSION NR: AP404~i;6~30 s/al~,~/6~. 007 0a~ 020 �
/ / / z/o2o~
TITLE: Elect,,ron absc,~rption spectra and stability of monotypic c
plexes ~ , ;.
.
AUTHC?R: l~erezin, _$. ~},,
f .r.. ... .~. .. ~
1 SOt~RCE: xVllZ. Khimiya i khimicheskaya tekhnologiya, v. 7 no, 2
,; � ~ l~b~. ~ 202-2C~~3 ' ,
z
;�
'~ 'TOPIC TAGS: electron; absorption spectra, spectral band shi~'t, cycl~.c
'~~ ~ pi~ligand, phthalocyanine, porphorin, coordination com}~xex, tetra-
phenyl.,porphorin, s3.gma bond strength, pi bond stren~?th, hypsochrom~,c~
shift
1
~ ABSTRACT: The relationship between the stability of cor~- lexeg and
the position of their absorption bands was investigatedpby examining ,
in detail the shift in thg absorption band in cyclic n ~ligands
with phthalocyan~.ne ,end porphorin upon coordin~-tion with different
. ;metal ions. The shift in the long wave bands of the spectrum of
phthalocyanine Fig. lj on complexing with Cu in a -chloronaphthalene
is attributed -~to the n~~ transition. In a y p, ~ iS -tetraphenylporphin
~�Fig. 2 ~ bands xI an,~ lV arecaused bytt-+~~~ tran$ition~ while the
Card l~~ ~
� :~
� - j
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ACCESION NR; AP1+o252b3 r ~ _ _.... _ _ _ .._ .._. _. ...._. __ . _ _.~~
4 i
;1956} a tbeoreti,.al arialy->is of the process of reprecipitatian of phthalacyaninn
pigments (prirnari].y in tha; `example of CuPQ) was conducted. Optimum cancL�.tions
i for their solution and su:.~ uric acid cons
of pigments are found. umption zequired for the full, solution
V+4~l.ues far sulfuric acid consumption kilogram) :needed for
the total. solution of l04 kg. pigment of blue phthal.acyat~~~~ae ~aa'lculated for ~ urn
p
.G~c.) are given for ltd ani;l SO C. Tt fal.lows from the data, that in the process
of reprecipitation of,, pign-ent from H2SO~ solutions with less thaal ~ 9~+~6 concentrate, n,
l~ ~
only a small part ai' the I~' @nt 3.s eagaased 'to the solution and consequently is 0
j converted into d-form; a l:~asic part of the pigment to micracrystal de ree i
B-farm. Orig, art. has: fit, tables. $ i $ ~ +
~ �, 1
ASSOCIATION: Tvanavskiy l+;himiko-tekhnologichesk~.y institut (Tvar~av Chemical
Engineexing Institute}; Ka,fedra anal.iticheskay khimie, (Department of Analytical.
C:~emistr`y}
' O'CfiTED: 420ct62 '' DA'~E ACQ: lOApr6~.
SUB CODE: Gg .
j loo. RED'. 34V. OtC1
E �~ ~
i
Card _ 2~2
_ .~ ~.
ENC~: 4O

"~ 3
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AccESSro~r NR: AP4o25263 s/o~.S3/63/00~/oo~iloi~/lo~.
AU'I'~ioR: Berezin, B.D.
~~~~�~
TSTLE: Physico-chemical. ,properties of phthalocyanine pigments
2. .Processes of dissol.v3,~;~g phthalocyanines in sulfuric acid and its derivatives
SOUREE: IYUZ. Khimiya i khimichesk~yra tekhnologiya, v. 6, no. 6, 1963, 1016-
1021
j ~.'oPrC TAGS: Phthalocyani~ie pigment, phthatocyanine, salfuric acid, phthal.ocyanine
dissolution
ABSTRACT: Under industri~;~,l and laboratory conditions, phthaloeyanine pigments
containing metal are most;J,y obtained using dry methods. For this
metals and their chloride~~ or oxides are coalesced with the hth~p'curpose, the
a mixture contain' p yanine'or with
a.ng phtha:Sic anhydride, urea and a catalyst. The reaction product'
is an extremely complex m:ixtus~e. The chemical a,etivity and thez~nodynamtcs of the
reprecipitation processes of industrial fusions of phthal.ocyan+~ne from solutions off'
sul~.ur, : hlorosulfonic ea;;id and fumi sutf'~ric acid.are examined. Based on a
previously given thermody~:~amic xation~F. Baumann et al. Angew. frhem. 68, 3,33, `
Card 1,/2
� t
_ _..._.._......_______ ...,,..__.._....___.. __.. ,r_ .._._.w ..._.__._ ._.___' ..._ _...~ _, .. ., .... .. i
~.
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Study of metal ...
ASSOCIATION:
s/o7~/~7/o~6/aa3/aa3/o11
~r, B101/B10b
by CauUheY, A. Cortva,n gee be
of metallic ethio or ~` to-v) about the mechanis�~ of deco,.
fi ~2res ~ P~Yrzne complexes axe called erroneous, Ther~osition
most rectnttreferenc~a ~~ references:
Soviet and a .ire 'T
Cr'� Cau he O ~n~~;lish-lan 5 non-Sov:i~et. The four
~ Ys A. Corc4~in, .,1, Amer. Chem.6~o~o f~ublications read as follov~~s:
U. Frye, R. Linsteud
A� Doak R. Lin$tead' J~ Chem. Soc. ' '~' 15a9, 1955f P. Barrett,
' . J. Chem. Soc. 0 1157' 1 ~~S' J � Anderso~a, Ii. .Sr~idhroolc,
F'. Handal ~. ~ C. Tiny, J . Chem. Sae. , ~ 1079 ~ ~ 1 1 ~3n i ~'. Barrett r R. Liras teal
~ 94a. r
SUBMITTEDt
Cuz+~ ~/3
Ivanovskiy khimiko-. tekhnologieheskiy
tote of Chemical Technology)
May 25, 19+~0
institut (Tvanova Insti_
.~
4.d
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Study of metal ... s/~7b/~?/~3~/c-o3/~03,~~11
B1o1/~1oe
. hour) at room temperature even in d:tluted HZa"OA . The unst~~hle :;Pc,~s .a
constants of h ~drol ~ hwd
,Y y~atian rate different from that of H?Pc (p,137�O,OOS
ner hour)',by one order ;~f magnitude. U*like the unstable ;~;Pc's v~rYzose 5
shocr� only the absorptia~~ bands of HePoH , tho stable t~2Pc's dis~a pa~ra
tion bands of their avm� Hydrolysis proceeds as I-iPc + Fi SO -~ iaPcfd}ab.~orp-
+ H2S0~ (2}, ir;Pcfi+ + 2H,,0+ 2} hi2+ + H PaH+ ~ sd 2 ~ `
I aq ? (, } i HZPcH+ ~- 3H a0 + 5fiZ0 v ~ ~ ,~~,~;
d~,~eompasition p~�oducts ~,~}� ~~ar stable MPo's, the reaction
~. (3 } is limi t~.n~~
which prooeeds aaoordin~;; to -dc /dt = k c ~
1w9Pc MPc itlPccH3U+~ cvhilc~ for the unsts;~.c3
i~~ro's, the reaction (3} proceed; rapidly and the reaction
that p (4) slowly, For
~rou the kinetic e~quatian as found for H2Pc is -dc, /dt
~ For the drol eie of H Pa in ~ h~Fc
kH2PecblPc�H~0+ ~' y ~ 7.7 M H SO the aetiva-.
tion energy was found to be 1 2 ~
9,500 cal, for the reaction Cl2SnPcH+ + 2H~'
-~ H2PcH+ + Sn~~ ~. 2Cl- it was found to be 21,700 cal. Tha a$g
Card 2/3 umptxons made 1
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~~o7G/~?/o~~/p0~/oc~3ja~~
B~ 01 ~J3108

AUTHOR: Berr- er za.n ~ ..B.~.~R__
TITLE; Study of metal phthalooyanines in solution. Vi. Effect of
' the natu Y~e of the central ion cn the strencth of the phthala-
cyanine n',acra-ring in sulfuric acid solutions
PERIODICALi Zhurnal ~''izicheskoy khimii, v. 36, na. 3, 19G2, 49:~ - 501
TL~'XT: The stability oi:' the compounds ~rlPc of phthalocyanine (H~Pc) .=rith
Cu2~ Ni2~, Cot*, Zn~*., 5n~+, Sn4~, A13~, V0~*, Cd2~, Pb2~, t;g2+, A{~~, Fe3*
as well as of thQ chlo~~inated eompaunds C115PvCu in 12 - 17.7 mole liter
H2S0~ was investigated at 25 - G5�C. The compounds can be divided into two
2+ 2+ Ni2+ Zn2*, ~1.13~, V02*, v~rhich { :.
groups: (1) stable cpnrpounds of Cu , Co , ,
displayed no noticeabl+~.~ dissociation at raorn ternperaturc, {2) unstable
compounds of Mg2~, Cd~~~~, Ag+, Pb2�, Fed*, Sn2+, Sn~'+. The stable tiPc's
and Cl15PcCu had very :3mall constants of hydrolyzation rate (k ~.1C-4 per
Card _ 1 f 3_..___~..__._.~~ ..... _ .....~...
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btethods or investigrxta.rl~ ...
~~ i ~~~
x/`020 6 i/ t t~ 1/002/013/02 7
}3103110
Ref. 70 t2, 6-`il~.it0nat~, Chain, I~~;~v.:i, ~'_ ~:':y)t) (1,~~f.~), ~,F C. 100 '~V. Cau~hey,
~. Corwin, J. Am. Chc.~n~.. 5oc., ~", 15~7~ (1~j); i~ef. 160 N. Ii~~ria, R. TaI'v,
~. Am. (;hem. Soc. ~6, 21~G (1);~.~-
ASSQCIA~'iiJN: Ivano~rsk:Gy kh~.mikawtekhi.c~l.c~gi.cheski,y~ instttut (Ivanova
Znsti,tut0:~ oi' Che~niaal 'i'ECl~nolnt~;y)
PR~;SENT''U0 June 23, i~61, by A. P1. 'rez~enin, academician
sv~,~aiTT ~~1? 0 June z~, 1 q61
`SablA 1. PR of the etguilibrium con,tantA of reaction (3) of stable
phthaloc~ranins at 25~~C.
Legend: (1) Phth~~.locyanin.
Table 2. Ti;mpnratu0'~: depc~ndencn o.f pK o� phthal.ocyanins in HZ90~.
r egr~nd: (1) Tempe~�tttt~.xe, �C; (2) pK of phtha~.oc;yanins of metals,
Card 5/~' `~.'
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~o~a~
s/o3~/~~/~~~/aoz/o~ ~/oz~
Methods of investiga~ting.Q, B10 Hi10
the same manner as free Pc. The hydrolysis a.t H2PcN* is complicated,. The
hydrolysis meohe,nism of stable MPc Has studied with the most unstable MF'c:
(HSO~)~SnPo o The by+9xolysis also fol],aws the equnt~,on I~A~~' Mi'~ + nA~ (1 ~.
The limiting stage inn unstable Po, howevery is the hy~ral~sis of the
H2PoA~ Aearox~ingq wh~~reaa in atabl,e MPo it is the costal separation (2a).
Thusy four ooordinat~: bands between metal and nitrogen are ruptured. The
hydrolysis of stable Pc is only naticeable~ at X00 ~- '!20�Cv As to the
readiness of separat,lanaftheoentral ion in Pc~ the metals farm the order
Co ~ Ni ~ Pd } Pt ~ At the same times the basis
properties of the fo:ar N atoms of the rings participating in (z) and (2a~
are increasingly neu~:ralizeda Pt2+ has tha highest stability, but also
(H504) A1Pe is very ;:stable. Tht above orr.er reflects the stability order
in or h rin com lex~:;e � 2+ ~~' 2+ z+ 2+ 2+ 2 2+ 2+
p p y p ~a ~ ~?g ~ ~4n ~ Fe ,} ~n ~ Cu > Co +}Ni ~lPd .
There are 6 tables a~td 78 re.~'ex~r~~~~a ~ 12 Soviet and 6 non~Soviet. The
three references to l~~nRl~ sh ~�1~- ~~ : ~:;~ plabl~.c;at ion; rc,s~, a~ .;'allows a
Card 4/~` ~'
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' s/ozai~~;~~~/oat/o~3/027
p,~ -`hods of investigating. o. L IG3/~~ ~~~
S~.nce the aonstanta .remain unchanged at all temperatures9 cancentrated
H254~ is an ideal aolventtl Thusg the ratio of acti~-i.ty coefficients of
the reactants ~.n (3) also remains constants and trre reaction productp
(MPcH)HS0~9 is completely dissociateda ~6PcH+ predominates in sulf uric
acid solutions o Th.e equilibri~~m constants pK of reactinn (~~ allo+~ cori-
clusions ag to the formation and durability of 6,o and n-bonds, the
stability of ~iPcs the existence of an excessive charge on the cen~,.c~a1 ian,
and the induction effect of the substituents in the benzene rin~~ `Phe
effect observed is an endothermic anP which decreases with increasing
solvation ability of Pcy either because of the ability of additional co-
ordination of the central ion (ZnPc~ ZnPeCl}9 or due to a charge of the
central ion (+A1PcC1}, or the palarizati.on of bonds in the chlorination of
benzene tinge (CuPc~115}o Pc disintegrates in gulf uric acid solutions
and i$ completely hydrolyzed on the macroring�
tHiCktPJ}H}~+6HQ+3H+---~-~QGH4N+q~1H~+Ho The coloring of
2' 8!}24 Z 652 +~ 2
YPeH+ and H2PcH+ dis.appearso All unstable Pc were found to hydrolyze in
Card 3/~
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Ddethods of in~eetigatirtg. ~.
,~~~1~~.
,~ y'
r ~.
h ~ t ,.;,~ ~ ~ ~ ~ f ~oz/�~ 3/07
of stable ~'a formed by Cut*y Zn~~9 Co`~ ~, ~~� n was dever~.~ined ~~~.b1e ;~}. irr~~~rersibz~.ity o"~~
I > in acid ~t~~ueous so:~ut~.ons m~~y be assuL~ed on t:':rG b.t is oA' ~~~; 3:~,i r~~ ~ `:jl,;-
by tree usual solubilit�t method of the dis:;oc:it~tian of ie;.;~ c,t~;~lt~ _c a~
1Vl~xj, Cpl, Cd, Hta, A~,, Yb, ~,nd F'e~. r,~en with the stable campoun:l ~~.'~~rc,
complete "rva.shing cut" of the metal with 1 mole of acid occurred of tE~^
~3 - 1U ds.y~s, with ~i~Pc and l'ai'c it occurr~;d a,fttr 4G - '?~? hr, r~it;i ~~gii~'c
of�er 120 hr, witl-~ HgP~ and CdPc after 12 - 1 ~j hr, and .,iti ~ ,y ~ f`.=r
- 3 hr4 The x~tte of ~vashing depends an tale t', ,,e of central icr.. ~'-
increases as the acid ~onecntr~Ltion increases, but it is ~iuan~itati~ ~~.;;
indeuendent of i:he H a.on concentration. It ~x�obably depends on tine
different rates of rupture of the donor - a~~cepfor bond betvre~~n :nc~+ ~t
~,nd addendum Presumably, it is the higher the lo~rer thn cov~~.':~nc
character of the metal -addendum bond 'It is due to r~s~..iual bs.sc
properties of inner-cyclic t1 atoms of the macro-Tint, since �lo b~.s.c�
properties of the addendum decrease as the firmness of the 6~-bond of
metal - nitrot;;en ~ncreases~ ,s retards filling of ti~~~ t~,~brid orbit
ti;e rneta.l ion b;~ electron pairs of nitrogen, ti.e 7011o~`+in~, se~;u~no:~s i
bond f'i~~�mnese rare givE n . ~~ rv ~ 11U ~ ;~i~; _ , t'b ~ Cd , tit, ~ C~~ ~.:.>:
Cdtd ~~~ y

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~11U~:131~7
~.,~'~~1'Ll.`i ~t,u~~ V1 4 ~~~ _t3 ~~;.~U1~~ Is~ n.~, ~?iit LiCl..i.OC~~l.d 1.Il ~_~wl ~~~.` ill.3 ~,... ~;; .,u
~olut inn
~;/FZ~iUIJiCiL: Zhurnal ~~~~ox~;wnic~ieskny kliilnii, v,: ;~o :fin 1~', 1c~1, 't~~ _ ~:i.",
~'~X'i': The e,uthnx s-audied le:;s ~.t~blc' ~~~llt~~l~slo,~,;
~o:ltib~.~.:ity lneti~od, ~~nci ~;i;ab?.c: ones by ;l:F:}aa~~ o~ z.aotc~~~~c ~:~ec'u;.tl;;~;~ '~ ;~:.~
c~ucUm~;o;~itinn of less st;abl~; Pc follo~vs the reaction ;,;lc ,-~~H,(i ~_ .~.Y._`~_ '
so:. ;~
E,l c::~acy. i,ii~~