Tap chi KHOA HOC DHSP TPHCM Sd 30 ndm 2011
T 6 N G
HgfP, CAU TRUC CUA MQT SO PHlTC CHAT CUA PLATIN(II) CHlTA
P H 6 I T\SAMIN
Dl/ONG BA VO*, NGUYEN TH| MINH THOY", NGUYeN KIM DI^M MAI'"
T6M TAT
Bon phirc chdt ciia platin (II) chita amin (4-methylpyridine, aniline, indole) dd dugc tdng hgp. Thdnh phdn vd cdu triic cua chiing dugc xdc dfnh bdi phuang phdp phdn tich khoi lugng phd UV, phd IR vd H-H COSY.
Tir khda: phiic chat platin (II), phiic cis-diamin cua platin (II).
ABSTRACT
Synthesis and structure of some complexes of platinum (II) containing amine ligand Four complexes of platinum(II) containing amine (4-methylpyridine, aniline, indole) were prepared. Their structures were examined by elemental analysis, UV-Vis, IR and NMR spectra.
Keywords: complexes of Pt (II), complexes cw-diamine of Pt (II).
1. Mif ddu
Phiic chit ciia platin ddc bift Id c/>[Pt(NH3)2Cl2] dugc dilu chl tir KsfPtCU] da dugc biet den nhu mdt dugc pham cd tinh khdng u cao vdi ten dugc phdm Id c/.splatin.
Tuy nhien, do c/^platin cd dgc tinh cao nen cdc nha nghien ciiu da tim cdch thay the cac nguyen tii clo trong K2[PtCl4] bdng cdc amin (Am) cd cdu tao khdc nhau de cd phiic chit dang c/5'-[Pt(Am)2Cl2] (dang amin khdng hdn tap) ho$c cw-[PtAm'Am'Cl2] (dang amin hdn tap), vdi hy vgng tim ra phiic chit platin mdi cd khd ndng khdng u cao md co it ddc tinh hem. Trong pham vi bai bdo ndy, chiing tdi trinh bay kit qud tdng hgp va nghien ciiu clu tnic bdn phiic chit thu dugc khi cho tuomg tdc giira K2[PtCl4] vdi 4- metylpyridin, indol, anilin tao ba phiic chit dang khdng hdn tap gdm cdc phiic Pl:
[Pt(4-metylpyridin)2Cl2], phiic P2: [Pt(indol)2Ci2], phiic P3: [Pt(anilin)2Cl2]; vd tuong tdc ciia K[Pt(anilin)Cl3] vdi indol tao mgt phiic chit dang amin hdn tap la phiic P4:
[Pt(anilin)(indol)Cl2j.
2. Thuc nghifm
2.L Tdng hgrp cdc phiirc chdt cis-[Pt(Am)2Cl2j (dang khdng hdn tap)y gdm cdc phirc Ph P2, P3
Tong hop phiic chit Pl: Cho tir tii 2 mmol 4-metylpyridin vdo dung djch bao hda mdu dd ciia Immol phiic PO: K2[PtCl4]. Khuiy dung djch phdn iing d nhiet do phdng,
TS, Trudng Dgi hpc Su phgm TPHCM
Tap chl KHOA HOC DHSP TPHCM Dumg Bd Vu vd tgk
sau khoang 30 phiit xult hien kit tiia vang nhat. Tiep tyc khuiy them nhilu gid niia rdi lgc ket tiia. Riia kit tiia bdng dung djch HCl 0,1N, nudc vd etanol lanh. Hifu suit dat khodng 75%. Sdn phim dugc kit tinh l^i trong rugu:nudc (1:1).
Tdng hgp phiic chit P2: Cho 2 mmol indol vdo dung djch bao hda mdu dd ciia Immol phiic PO: K2[PtCl4j trong etanoLnudc 1:1. Khuiy dung djch phdn iing d nhift do tir 30-35°C, sau khodng mOt gid xult hifn kit tiia vdng sdm. Tilp tyc khuiy them nhilu gid niia, lgc kit tiia. Riia kit tiia bdng dung djch HCl 0,1N, nudc vd ancol. San pham dugc kit tinh lai trong rugru:nudc (1:1). Hifu suit dat khodng 45%.
t r
Tdng hgp phiic chdt P3: Cho 2 mmol anilin vdo dung djch bao hda mdu dd ciia Immol phiic PO: K2[PtCl4j trong etanoLnudc 1:1. Khuiy dung djch phdn iing d nhift do phdng, sau khodng 15 phiit xuat hifn kit tiia vdng sdm. Tilp tyc khuay them 3 gid nira roi lgc, thu kit tiia. Rira kit tiia bdng dung djch HCl 0,1N, nudc vd ancol lanh. San phim dugc kit tinh lai trong rugru:nudc (1:1). Hifu suit dat khodng 50%.
2.2. Tdng hgrp phiirc chdt hdn tgp P4: fPt(anilln)(indol)Cl2j
So dd phdn ling: K2[PtCl4J + anilin ^ K[Pt(anilin)Cl3] (PO) + KCl (1) K[Pt(anilin)Cl3]+indol ^ [Pt(anilin)(indol)Cl2] (P4) + KCl (2) (1) Tdng hgp chit PO': K[Pt(anilin)Cl3j. Tiln hanh khdc vdi tai lifu [1], chiing tdi da thuc hifn phdn iing voi phdi tii anilin dugc axit hda. Cho 5 mmol anilin da dugc hda tan trong dung djch HCl 0,1N vdo dung dich chiia 5 mmol K2[PtCl4]. Khuiy dung djch phan ling tren bIp each thuy, d nhift do 60-70°C. Khuiy khodng 10 phiit, bdt ddu thiy ket tiia xudt hifn. Dun va khuay khodng 30 phut nGa dl kit tiia hodn toan. Lam lanh dung djch. Lgc ket tiia, thu dugc dung djch dong nhdt mau cam. Cd can, kit tinh, thu tinh the, nia bdng axeton. Hifu suat khoang 72%.
(2) Tdng hop phiic chat P4: Cho 1 mmol indol vdo dung djch bao hda mau da cam ciia 1 mmol phiic K[Pt(anilin)Cl3] trong etanoLnudc (1:1). Khuiy dung djch phdn iing d 40°C, sau khoang 1 gid xuat hifn kit tua vdng. Tilp tyc khuay them 4 gid niia. Lgc ket tiia, rira ket tiia bang dung djch HCl 0,1N, nudc va etanol lanh. Sdn phdm dugc ket tinh lai trong etanoLnudc (1:1). Hifu suit dat khodng 40%.
2.3. Xdc dinh thdnh phdn vd cdu true
Vifc xdc dinh ham lugng Pt dugc tiln hanh bdng phuomg phdp trgng lugng tai Phdng thi nghifm dai cuong, Khoa Hda hgc, Trudng Dai hgc Su pham TPHCM.
Pho IR dugc ghi tren may FTIR - 8400S - SHIMADZU tai trudng Dai hgc Su Pham TPHCM.
Phd hip thy electron cua cdc phiic dugc do trong dung mdi thich hgp vdi ndng do bao hda cua chiing tren may PERKIN - ELMER LAMBDA 25 UV - VIS SPECTRUM tai Trudng Dai hgc Su pham TPHCM.
Pho ^H-NMR va COSY dugc do tren may Bmcker ADVANCE (500MHz), trong dung mdi DMSO, tai Vifn Hda hgc - Vien Khoa hgc Cdng nghf Vift Nam.
Tap chf KHOA HOC DHSP TPHCM Sd 30 ndm 2011
3. Ket qua v^ thdo lu^n
Phirc chit PO cd mdu dd tia, phiirc PO' cd mdu da cam, cdc phiirc chit Pl, P2, P3 vd P4 cd mdu vdng nhat ho^c vdng s$m.
Kit qud phdn tich hdm lugng nguySn t6 platin dugc lift ke d bdng 1.
Bdng 1. Hdm lugrng nguyin tS platin cua cdcphdtc chdt
Phirc chit
rPt(4-metylpyridin)2Cl2]
[Pt(indol)2Cl2]
[Pt(anilin)2Cl2l [Pt(anilin)(indol)Cl2]
hifu Pl P2 P3 P4
Pt i % Khoi Ivgrng) thuyet
43,14 39,00 43,14 40,97
Thyc nghifm
44,39 40,06 40,39 41,22
Bang 1 cho thiy kit qud khd phii hgp vdi cdng thiirc dy kiln ciia cdc phirc chit Kit qud phdn tich ph6 IR dugc dugc lift ke d bdng 2.
Bdng 2. Cdc vdn hdp thg chinh trin pho IR cua cdc phuc chdt tdng hgrp Ki
hifu
Pl P2 P3 P4
VNH
-
3215 3132 3200 3126
VcH
thom 3095 3016 3066 3060 3045
VcH
no 2918
-
SNH» VC=C
thom 1618 1610 1587 1600 1599 1587
8c-H no
1500
-
-
-
vc=c thom 1437 1377 1469 1454 1396 1467 1465 1437
YCH
thorm 812 717 785 765 756 721 756 690
Vp,.N
505 440 574 451
Tren pho IR tir Pl-f-P4 xult hifn nhumg vdn phd ddc trung cho dao dgng hda trj cua Vpt.N d viing tan so 505-^440 cm'' Dilu ndy chiing td cdc amin da tiiam gia tao phirc vdi Pt(II), vd sy tao phiic dd tiiyc hifn qua nguyen tir Nito.
Cdc van hip thy chinh tren pho IR diu d$c trung cho nhdm nguyen tii trong phdn tii ciia cac phiic chit.
Khdc vdi phd ciia Pl, P2, pho cua P3, P4 (chira anilin: amin bac 1) da xult hifn cac vdn pho d vimg tin sd khodng 3215-^3126 cm"' ddc trung cho dao dgng hda trj VN-H-
Tap chf KHOA HOC DHSP TPHCM Duomg Bd va vd tgk
Dl khdng djnh them kit ludn tren, chiing tdi tiln hdnh do phd UV-Vis. Cdc van hip thy tren phd electron ciia cdc phirc chit tdng hgp chi ra d bdng 3.
Bdng 3. Cdc vdn hdp thg trin phd eletron cua cdc phirc chdt tdng hgrp dugrc
Phuc chat PO: K2[PtCl4]
PO': K[Pt(aniline)Cl3]
Pl:[Pt(4-Me-Py)2Cl2]
P2: [Pt(indol)2Cl2]
P3: [Pt(anilin)2Cl2]
P4:[Pt(anilin)(indol)C I2I
Dung
A •
moi Nudc Nudc Rugu Rugu Rugu Rugu
Mdu Dd tia Da cam
Vdng Vdng Vdng Vdng
)J\ogz
216/3,99 206/4,70 205/4,8 213/4,52 205/4,69 213/4,64
243/4,01 241/4,18 264/3,97 260/3,70 265/3,97
-
299/2,79 291/3,98 287/3,85 299/3,40 281/3,94
330/1,8 476/1,20 375/2,21
• -
Pho UV-Vis ciia tit cd cdc phiic chit trdn diu gidng nhau d chd ciing thi hifn van phd cd cudng do ldn trong vimg 205- 216 nm dugc quy cho van thi hifn sy chuyin muc kem chuyin difn tii tii phdi tii Cl tdi ion trung tdm Pt^^ Ben canh dd, sy khdc bift vl phd giiia chiing dugc thi hifn rd rdng qua vifc PO khdng cd cdc van hap thy viing 240- 299 nm la cdc tin hifu ddc tnmg cho chuyin mirc n-^n* o nhan thom ciia phdi tii [2]. Qua dd cho thiy, cdc phdi tii amin cd nhdn thom da di vdo cdu phdi tri ciia Pt(n) khi tiromg tdc vdi PO. Cdc phiic chit Pl, P2, P3, P4 rit it tan ti-ong nudc va it tan trong ancol. Do do, chiing tdi chi ghi dugc phd cua chiing vdi ndng do bdo hda lO^M trong etanol. Trong trudng hgp ndy, vi dung djch qua loang vd mdu rit nhat nen da khdng ghi nhan dugc vdn phd thi hifn chuyin miic d-d d ion Pt^"^ Vdi phiic chdt PO vd PO' do tan khd tdt trong nudc vdi ndng do bdo hda khodng 10"^M thi da xult hifn cdc vdn phd khodng 330- 375 nm vdi cudng do thlp. Theo tdi lifu [3], chiing da dugc chiing tdi quy kit la vdn iimg vdi chuyin mirc d-d ciia ion Pt^"^ Sy khdc bift giua cdc phiic vl su cd hodc khdng cd van phd trong vimg nay (vimg 330j 375 nm) ciing da phdn dnh su phu hgp vl mdu sdc dam hom ciia PO, PO' so vdi mdu sdc nhat hon ciia Pl, P2,P3vdP4.
D I xdc dinh clu tnic ciia phirc chit dugc rd rang bgn, chiing tdi tiln hdnh phdn tich phd 'H-NMR va H-HCOSY cua cdc phiic chit PO', Pl, P2, P3, P4. Phd H-HCOSY ciia phiic chit P2, P4 dugc gidi thifu d hinh 1. Kit qud phdn tich phd tin hifu proton dugc lift ke 0 bdng 4. trong dd: Pl, P2 vd P3 chi chiira mdt loai phoi tii amin, cdn P4 chiia hai phdi tii amin khdc nhau.
Tgp chi KHOA HOC DHSP TPHCM So 30 ndm 2011
Pt CindoJ;3CL2-OHSO-COSYOP
THUY-PJ-CHSO-COSraP
a) b) Hinh L Nhitng diim tutmg ding vd khdc bl^tgiitaphd COSY cda P2(a) vd P4(b)
Bdng 4 cho thiy dg chuyin djch hda hgc ciia cdc proton cua phoi tii trong phirc chit cd gid trj thay ddi so vdi tin hifu proton cua cdc phoi tii ty do [2]. Dilu ndy la do da cd sy phdi ti-i giiia N ti-en amin vdi Pt(II). Qua dd, sir gidm mat dg electi-on da lam tdng dg chuyin djch hda hgc mgt so proton. Mdt dilu thu vj la dg chuyin dich hda hgc cdc proton trSn indol trong phirc chit (P2, P4) cd gid trj khdng khac nhilu so vdi vdi do chuyin djch hda hgc cdc proton ciia indol ty do.
Bdng 4. Dp chuyin dfch hda hgc cdc proton cda phoi turL tu do vd trong cdc phurc chdt
Chit Pl 4-Me-Py tvr do P2 Indol t\rdo P3 Anilin t\rdo
Ph6i tir ^ ^ > - ^ ^
) 1
•<X5:
3 2
S 6
H2 8,58; dd
H3 7,32; dd
H4 H5
7,32; dd
H6 8,58; dd
Hkh^c 2,41; s Chura tlm thiy s6 li^u thvrc nghifm
7,32; t 7,26 7,25; d
6,46
6.41; t 6,45 7,20; t
7,01
7.53; d 7,55 7,11; m
6,62
6,97; t 6,99 7,20; t
7,01
7,07; t 7,09 7,25; d
6,46
H7:7,38;d H7:7,4
T9P chf KHOA HOC DHSP TPHCM Duorng Bd Vd vd tgk
P4
Anilin trong phuc P4
3 2
5 fi.
H2
7,21; d H3
6,76; t
H4
7,13; t
H5
6,76; t H6
7,21; d
Indol trong phuc P4
H2'
7,32; t
H3'
6,41; s
H4'
7,53;d
H5'
6,97; t
H6'
7,07; t
Hkhac (H7')
7,38; d
Dieu dd cd the gidi thich Id do mat dg electron vdn khd ldn trong vdng indol da khdng bj dnh hudng nhilu khi N ciia vdng ndy phdi tri vdi Pt(II). Dilu dd ciing ddn din vifc cdc tin hifu proton ciia indol trong P2 vd P4 diu thi hifn rd rang vd rit tuong ddng nhau. Ciing nhd vay, chiing tdi dl ddng ngoai suy de xdc djnh tin hifu proton cua anilin trong phiic P4.
CJ phirc chit P3, P4, tin hifu proton ciia anilin cdn thay ddi trdt tu dg chuyen djch ciia H2, H6> H3, H5 (trdt tu d anilin tu do thi ngugc lai).
Bdng 4 ciing cho thiy su khac bift rd rft giiia tin hifu proton ciia anilin d P3 vd P4. Dilu ndy cd thi gidi thich la do indol la mgt phdi tii cdng kinh, dn ngir khdng gian ldn, nen da tuomg tdc vdi anilin dnh hudng manh din do chuyin djch ciia H3 va H5. Cd till d ddy, indol da lam gidm sy chdn bit ddng hudng (tinh phdn chdn) tren vdng thom ciia anilin, ldm cho H3 vd H5 chuyen vl trudng manh hom so vdi cdc proton cdn lai tren anilin trong phirc chit.
4. Ket luan
Da tdng hgp dugc cdc phiic vudng phdng ciia Pt(II), gdm:
Pl : cw-[Pt(4-metylpiridin)2Cl2], P2 : cw-[Pt(indol)2Cl2j,
P3 : cw-[Pt(anilin)2Cl2], P4 : cw-[Pt(anilin)(indol)Cl2].
Trong dd cdc phiic chit P2 vd P4 chua tim thiy trong cdc tdi lifu tham khdo.
Da dung cdc phep phdn tich hda hgc ddc tnmg de xdc djnh thdnh phdn vd de xuat clu tnic cua 4 phiic chit nhu sau :
^'% .v-CI
y\
c«-di-4-metylpyridindiclopIatin(II) Pl
m-diindoldicloplatin(II) P2
Tap chf KHOA HOC DHSP TPHCM Sd 30 ndm 2011
Cl/.
\ .i f .Cl
cu ^^
'% # .Cl ,'pt"H , N ^ \
cu-anilinindoldicloplatin(II) ci5-dianilinedicloplatin(II) P3
2.
3.
TAI LIfU THAM KHAO
Nguyen Thj Phuomg Chi (2000), "Tdng hgrp, xdc dinh cdu true, tinh chdt vd thdm dd hogt tinh chdng ung thu cua mgt sd hgp chdt cis-dicloroanilinaminplatin(II), Luan an tiln sT Khoa hgc Hda hgc, Trudng DHSP Hd Ngi
Nguyen Huu DTnh, Trin Thj Dd (1999), Ifng dung mdt sd phuang phdp phd nghien ciru cdu true phdn tic, Nxb Giao dye.
Manfred Hesse, Herbert Meier (1997), Spectroscopic methods in organic chemistry, Geor Thiem Verlag, Smttgart, New York.
(Ngdy Tda soan nhdn dirge bdi: 18-7-2011; ngdy chip nh$n ddng: 03-8-2011)