Embed Size (px)
Citation preview
APPROACHES TO SELF-ASSEMBLED SYSTEMS BASED ON THE N-ACYLAMIDOPHOSPHATE COMPLEXES
N. G. Zabirov1, I. A. Litvinov2
1 Kazan State University, E-mail: [email protected] Arbuzov Institute of Organic & Physical Chemistry
Q
Q
Q Q
Q
Q
Q
QM
n+Q
Q
Q
Q
Q
Q
Q
Q- Mn+Q Q
Q
Q
Q
Q
Q
Q
Q
QM
n+Mn+
4
Q QZ
Q Q
Q QZ
Q Q
Q QZ
Q Q
Mn+
Mn+M
n+
Q
Q
Z
ZQ
Q
Mn+
Q
Q
ZQ
Q
Mn+
Mn+
Q Q
Q Q
ZMn+
+ +
X, Y = O, S
(1) R: Alk; Ar; benzo-15-crown-5
(2) R: NR2R3;
NH-Z-NH; aza- and diaza-18-crown-6; aminobenzo-15- crown-5.
Z: (CH2)m m = 2-7;
OHN NHn
n = 1-3
R1: OPr-i, OEt, Ph, OPh etc.
[1] N. G. Zabirov et al. Uspechi khimii, 1991, 60, 2189; [2] R. M. Kamalov et al. Uspechi khimii, 1985, 54, 2044; [3] T. Q. Ly, J. D.Woollins, Coord. Chem. Rev., 1998, 176, 451.
P
Y
NC
X
H
R2
1R
P
Y
NC
X
H
R2
1R
/n
Mn+
P
Y
N
M
C
X
R2
1R
{2}{2}
(3)
O O
N O
O O
O
OO
O
OO
OO
O
ONH
CN
X
P
Y
HR2
1C N
X
P
Y
H
R21Z
C N
X
P
Y
H
R21
CROWN
RC(S) NH2 R`2P(Y)Cl+
R`2P(Y)-NH2+
B:RC NH PR`2
X YRC(O)Cl
HN(CH2)pNH p = 2, 7; Z:
HN O NH m = 1, 2; m
O O
N N
O O
R R N C NH PX Y
<R R NH + X=C=N-PY<1 2 1 2
METHODS OF SYNTHESISMETHODS OF SYNTHESIS
(1)
(2)
{3}{3}
(4)
(5)
(6a) (6a) X =X = SS (6b) (6b) X =OX =O
O O
N N
O O
C
X
NPR 2S
C
X
NP
SH
H
1R2
1
(6)(6)
(7)(7)
1O
O
O
O
O
S
H
S
PR 2N
C
(7)(7)RR11 = OPr-i = OPr-i
{4}{4}
Trans-square M = Ni (II), Pd(II)
Cis- square Pt (II) {Y=S};
M = Cu(II), Pd(II) {Y=O}
Tetrahedron M = Co(II), Hg(II) {Y = S, O};Zn(II), Cd(II) {Y = S}
P
S
N
M
C
S
R2
1R
P
S
NC
S
R2
1R
P
Y
N
M
C
S
R2
1R
P
Y
NC
S
R2
1R
(4) (4) Zabirov N. G., Litvinov I. A., Kataeva O. N.Zabirov N. G., Litvinov I. A., Kataeva O. N. et al.et al. Russ.J.Gen.Chem. 1998,Russ.J.Gen.Chem. 1998, 19981998,, 99,, 1408. 1408.(5) (5) A A..LL..KonKon’’kinkin, , VV..GG. . ShtyrlinShtyrlin, , NN..GG. . ZabirovZabirov, , II..AA. . LitvinovLitvinov et al. et al. Phosp. & SiliconPhosp. & Silicon 1999, 147, 4491999, 147, 449..
RR = Ph = PhRR11 = OPr-i = OPr-i
(8)(8)C1-C2 C1-C2 9.9.66ÅÅ
(9)(9)C1-C2 C1-C2 88.0.0ÅÅ
RR = Ph = PhRR11 = OPr-i = OPr-i
{5}{5}
(С(Сo1), (Co2) o1), (Co2) NN.. G G. . Zabirov,Zabirov, FF.. D D. . SokolovSokolov, , VV.. V V. . BruskoBrusko, , II.. A A.. Litvinov, Litvinov, DD.. B B. . KrivolapovKrivolapov ( (unpublished workunpublished work))
C S
PN
S
Co
RR = Ph; = Ph; RR11 = OPr-i = OPr-i
((10)10)C1-C2 C1-C2 88.0.0ÅÅ
((11)11)C1-C2 C1-C2 8.958.95ÅÅ
P Y
N M
C S
R2
1
R
PYN
CS
R2
1
R{6}{6}
M1
CN
X
P
Y
R21
M1
CN
X
P
Y
R21
M M transition metal MM11, , MM22 alkali metals C
N
X
P
Y
CN
X
P
YM
R21
M2
R21
M1 P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1M
1
An-An-
C N
X
P
Y
H
R21
CROWN{7}{7}
(13)
(12)
(14)
O O
N O
O O
O
OO
O
OO
OO
O
ONH
C N
S
P
S
H
R21
CROWN
O
OO
O
ONH C N P(OPr-i)2
SSNa
O
OO
O
ONH C N P(OPr-i)2
SSNa
O
OO
O
ONH C N P(OPr-i)2
SSNa
m
M = Na+, K+
CompoundCompound (16b)(16b) is solubleis soluble only in very only in very polar solventspolar solvents ((HH22O, DMSO, DMFO, DMSO, DMF).).
(16b)
((aa)) ((cc))((bb))(15)
{8}{8}
O O
N O
O O
O
OO
O
OO
OO
O
ONHP
S
N
M
C
S
R2
1
/2
M = Ni(II), Pd(II), Co (II), Zn(II), Cd(II)
M = Ni(II); RM = Ni(II); R11: OPr-i; M: OPr-i; M.. p. p. 125 125°°C; C; 3131РР 50.0 50.0 ppmppm
((17a17a))
((aa))((1717)) ((cc))((bb))
((17a17a))
2HL + 2KOH 2HL + 2KOH 2LK + M 2LK + M2+ 2+ ML ML22 {9}{9}
{10}{10}
M = Zn(II); R: OPr-i; MM = Zn(II); R: OPr-i; M.. p. p. 114114°°C; C; 3131РР 53.8 53.8 ppmppm
((1818))
CR: aza-18-crown-6
(i-PrO)2
CR
C S
N Zn
P SPS
NCS
(OPr-i)2
ÑR
CN
X
P
Y
HR2
1C N
X
P
Y
H
R21Z
CROWNCN
X
P
Y
HR2
1C N
X
P
Y
H
R21
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
Z
Z
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
Z
m
P
Y
N
M
C
X
R2
1
P
Y
NC
X
R2
1
Z
Z
M = Co (II), Ni (II), Pd (II), Cu (II), Zn(II), Cd(II), Hg(II)
{11}{11}
((1919)) ((2020))
((2121)) ((2222))
RR11 = OPr-i = OPr-i
{12}{12}
((2323))
1R21
1R21NHC
NP
S S
CdSS
PN
C NH
HN CN
PR 2
S S
SS
PR 2N
CHN
Cd
4.2 4.2 ÅÅ
1R2
1
1R2
1NHCN
P
S S
PdSS
PN
C NH
HN CN
PR 2
S S
SS
PR 2N
CHN
Pd
O
O
RR11 = OPr-i = OPr-i
{13}{13}
((2424))
1R2
1
O O
N N
O O
CN
PR 2CN
P
S S S S
CoSSSS
PN
C PR 2N
C
OO
NN
OO
Co
1R2
1
RR11 = OPr-i = OPr-i
{14}{14}
((2525))
This workThis work have been madehave been made due to support of due to support of Russian Foundation for Russian Foundation for BasicBasic ResearchResearch ((grantgrant ## 00-03-32742 00-03-32742aa)) andand joint program of joint program of CRDFCRDF andand Russian Ministry of EducationRussian Ministry of Education « «Basic Research and High Education”Basic Research and High Education” ((grantgrant RECREC-007).-007).
Dr. Dmitry B. KrivolapovDr. Dmitry B. Krivolapov A. E. Arbuzov Institute of Organic & Physical Chemistry
• Prof. Rafael A. CherkasovProf. Rafael A. Cherkasov• Dr.Dr. Vasiliy V. BruskoVasiliy V. Brusko• Dr.Dr. Felix D. SokolovFelix D. Sokolov• Dr.Dr. Valery GValery G. . ShtyrlinShtyrlin• Dr. Luisa N. YamalievaDr. Luisa N. Yamalieva• Dr.Dr. Elvira GElvira G. . YarkovaYarkova• Dr.Dr. Sergey VSergey V. . KashevarovKashevarov• Mr.Mr. Alexander YuAlexander Yu. . VeratVerat Kazan State UniversityKazan State University
ACKNOWLEDGEMENTSACKNOWLEDGEMENTS
