Trinh Nggc Chau va dtg Tap chi KHOA HOC & CONG NGHE 83(07): 25-29
TONG HOP, NGHIEN CUU CAu TRUC CUA CAC PHlTC
C H A TNi(n)
VA Pd(H) VOI N'^'-PHENYL T H I O S E M I C A C B A Z I T
Trinh Nggc Chau', Nguyen Thj Bich Huong , Hoang Duy Cuong', Nguyen Thj Thanh' Khoa Hoa hoc. Truang Khoa hoc Tir nhien. DHOGIIN
'Trudng Dgi hoc Su phgm, DH Thdi Nguyen
TOM
TATPhan ung giua N' '-phenyl thiosemicacbazit (Hpth) va Ni(ll) hay Pd(ll) trong dung dich cd mdi trudng kiem vdi pH= 9-10 tao thanh hai phdc chat Ni(pth)2 va Pd(pth)2. Cac phirc chat da dugc nghien cdu bang phuong phap phan tich hoa hgc, pho IR, phd ' H - N M R , ' ' C - NMR va phd MS.
Ket qua thu dugc cho thay Hpth lien ket vdi cac ion kim loai qua cac nguyen td N'" va S de tao thanh cac phuc chat vudng phang, chua cac vdng 5 canh ben. Du kien pho ''C- NMR cho phep phan biet hai cau hinh cis va trans cua ca 2 phuc chat.
Til' khda: phenyl thlosemlcarbazide, N''''-phenyl thlosetnlcarbazlde, phirc chdt cua Nlfll; phitc chdt cua Pd(ll); phitc chdt vudng phdng
MODAU
Cac phirc chdt cua thiosemicacbazit va ihiosemicacbazon dd dugc nghien cdu tu rdt
Idu nhung ldi nay nd vdn dang ddnh dugc su quan ldm chu y cua nhieu nhd hda hgc trong vd ngodi nude [4.6]. Cdc nghien cdu trudc day dd chi ra rdng cdc thiosemicacbazit. cdc ddn xudt the cua nd vd phuc chat cua cluing cd nhieu ung dung trong cac ITnh vuc khde nhau nhu y hgc, ky thuat [3,5]. Ddc biet la khd ndng dc che su phdt trien cda te bdo ung thu [2]. Trong cdng trinh nd} chdng tdi trinh bdy mgl sd ket qua nghien cuu phirc chat cua Ni(ll) vd Pd(ll) vdi
thiosemicacbazit.
N'"-phenyl THUC NGHIEM
Tong hop phiJ'c chat cua Ni(II) va Pd(II) vol Hpth: Ni(pth)2va Pd(pth)2
Hod tan hodn todn 0.668 g Hpth (4 mmol) trong 20 ml nude cdt da hda lan 1-2 gigt HCl dac (mdi trudng pH: 1-2). cho tir lu dung dich NHi dac vdo cdc chira 10 ml mudi MCL 0.2M (2 mmol) (M: Ni. Pd) cho den khi mdi trudng dat pH: 9-10. Dd tu tu hai dung dich ndy vdo nhau vd khudy deu bdn hop tren mdy khudy lu, d nhiet do phdng se thdy xudt hien ket Ida mdu ndu ddi vdi phiic cda Ni(Il) \d ' /'('/, 01684 y.-^'^rxo
mdu vdng cam ddi vdi phuc cua Pd(II). Tiep tuc khudy them 3 gid nua de phan irng xdy ra hodn loan.
Lgc rua kel tua tren pheu lgc thuy tinh day xdp bang nude, bdn hop rugu nirdc. rugu vd cudi cdng bdng dielylete. Lam khd chdt ran thu dugc trong binh but dm.
Cac dieu kien phan tich
I lam lirgng cua cdc kim loai trong phdc chat dugc phan lich lbeo phuo-ng phdp trgng lugng bdng cdch cho ket lua vdi dimetylglioxim.
Phd hdng ngoai cua phdi td vd cdc phdc chdt dugc ghi tren may quang phd FR/IR 08101 cua hdng Shimadzu. Mdu dugc che lao theo phuong phdp ep vien vdi KBr.
Phd ' H vd ''C - NMR cua cac chat dugc ghi tren mdy Brucker - 500MHz, d 300K trong dung mdi DMSO.
Phd khdi lugng cua cdc phirc chat dugc ghi tren mdy Varian MS 320 theo phuang phdp ESI, che do do possitive.
KET QUA vA THAO LUAN
1. Ket qua phan tich ham lugng kim loai Ket qud phan tich ham lugng kim loai trong phirc chdt cho thdy trong phirc Ni(pth)2 niken chiem 14.93% (tinh theo cdng thirc phan tu gid dinh Id NiCi.tHu.Nf.S. Id 14.87%). phdc Pd(ptb)2. paladi chidm 24,29% (tinh theo cdng thde gid dinh PdC,,HKN(,S2 Id 24.37%). Nhu vdy. cdng thuc gia dinh cua phirc chdt la dung.
25
Trinh Nggc Chau vd dig Tap chi KHOA HOC & CONG NGHE 83(07): 25-29 2. Pho MS cua cac phuc chat.
De khdng dinh lai cdng ihirc phdn tu cua 2 phuc chat chung ldi da ghi phd khdi lugng cda chung:
Tren phd MS cua Ni(plh)2 vd Pd(pth)2 deu cd cac pic cd cudng do cao nhdl dng vdi pic ion phdn tu 391 cua NiCiaHioNhS: vd 439 cua PdCMHK,N,S2.
Vi cdc phan tu phuc chat deu chua cac nguyen td cd nhieu ddng vi ben nen cd the kiem dinh them mdt lan nua cdc cdng thdc phdn tu tren bang each so sdnh cirdng do cac vach phd thuc nghiem vdi cudng do li Ihuyel tinh Irong cum pic ion phdn tir. Viec tinh todn cudng do li thuyet cua cdc vach ndy dugc thuc hien online theo [7].
OLylhuyel
•Thuc le
Hinh L Cudng do tuong ddi cac vach trong cum pic ddng vi ( ion phan td) tinh theo li thuyet va thuc nghiem vdi cda Ni(pth)2 (a) va
Pd(pth)2 (b)
Kel qud Ihu dugc tren hinh 1 cho thay thdy giua thuc te vd ly Ihuyel khd phu hgp nhau.
Nhu vdy, cac ket qua phdn lich hda hgc vd phd MS cua 2 phiic chdt hodn loan phu hgp nhau vd cho phep khdng dinh cdng thuc phan tu cua 2 phiic chdt Id: NiCuH|6N6S2 (Ni(pth)2) vd PdCuHifiNoS. (Pd(pth)2).
3. Pho IR eiia phoi tir va phiic chat
Tren phd hap thu hdng ngoai cua phdi tu xuat hien ddi hap thu ddc trung cho dao ddng hda tri cda NH trong vung tir 3000 - 3500 c m ' nhung khi chuyen vdo pbiic chdt ddi hap thu ndy deu bi gidm ve cudng do. Dieu ndy duge gidi thich Id do khi tao phuc mdt nguyen tu H cua nhdm N ' " ' H da Idch ra, H lien ket vdi nguyen tu S nhung sau dd nguyen tu H ndy lai bi tach ra nhirdn^i chd cho ion kim loai.
tren phd cua cdc phuc chdt deu khdng xuat hien ddi hdp ihii ddc trung cho dao ddng cua lien ket SH d vung 2500 cm"'.
( 1 )
H:N^ ,2, NH
I
N S
( I )
H:N^ ,2, N
II
C IJ) HS N / \
H
dangthion dang thiol Nhu vay cd the ket ludn phdi tu tao lien ket vdi ion kim loai qua S. Trong phd cua phdi Id ddi hdp thu ddc trung cho nhdm CS d 895 cm"' cdn trong phd cua Ni(pth)2 d 759 cm"', cua Pd(pth)2 d 757 em"'. Mgl bang chdng khac nua cho sir thiol cua phdi tu khi chuyen vdo trong phuc chdt dd la sir xudt hien ddi hap thu ddc trung cho dao ddng cua N ' ' = C. So vdi phd cua cdc phdi tu tuong ung thi trong phd cua cdc phue chdt deu xuat hien ddi hap Ihu cua N'-' = C d 1589 vd 1594 cm"' lan lugt trong cac phuc chat Ni(pth)2 vd Pd(pth)2. Vi tri lien ket thu hai cua phdi tu vdi eac ion kim loai Id qua nguyen tu N ' " . Bang chung cho kel luan ndy Id sir chuyen vi Iri cdc ddi hap thu ddc trung cho dao ddng lien ket C = N " ' va CNN ve sd sdng thdp hon. Khi phuc chat dugc tao thdnh qua nguyen tu N' ' lam mat do electron tu do tren nguyen tu ndy gidm keo lbeo sir giam ve tan sd hdp thu cua dao ddng lien ket C = N " ' vd CNN. Ddi hdp thu dac trung eho dao ddng lien ket C = N ' " xudt hien trong phd cua phdi tu Hpth Id 1593 cm"
nhung khi chuyen vdo phuc chdt Ni(plh)2 va Pd(pth)2 thi vj tri tuong ung cua nd Id 1516 va 1514 cm"'. Ddi hap thu eua dao ddng nhdm CNN cung chuyen ve sd sdng thdp hon khi chuyen tu phdi tu tu do vdo phd cua phdc chat: trong phd phdi tu d 1441 cm"', gidm 10 vd 5 cm"' khi chuyen vdo phuc chdt Ni(plh)2 vd Pd(pth)2 tuong ung.
Tir nhung phan tich tren ehung tdi dua ra md hinh cua phdi lu vd md hinh lao phuc nhu hinh sau;
M: Ni. Pd
26
Trinh Nggc Chau vd dtg Tap chi KHOA HOC & CONG NGHE 83(07): 25-29 4. Pho H-NMR cua phoi tu va phuc chat
Cdc tin hieu cdng hudng trong phd 'H-NMR cua phdi tu va phuc chat dugc chi ra tren bang 1. Phd 'H-NMR cua Hpth vd Ni(pth)2 duac dua ra tren hinh 2.
<.<•^:/•
hieu cdng hudng singlet d 4,78 ppm dugc gdn cho 2 proton nhdm N * " H 2 trong phdi tu.
Trong phdc chdt chung tach thdnh hai pie rieng biet: trong phuc Ni(plh)2 Id pic singlet d 6,56 vd 6,32 ppm con trong Pd(pth)2 Id hai pic 7,58 vd 7,37 ppm.
Cdc tin hieu cdng hudng cda cdc proton khde thay ddi khdng ddng ke chung Id su lao phuc khdng dnh hudng tdi nhung vi tri ndy.
Bang 1: Cac tin hieu cdng hudng trong phd ' H - NMR cua phdi tu va phuc chat
yy * :
ia)
• <'*«»»<-.4<'.rf-);«'-'-- 'l
ll
„...:i
a '^^:W'
Qui ket (ppm)
N'-'H N'^'H H(ortho) H(meta) H(para) N"'H
Hpth 9,6(s,l) 9,l(s,l) 7,65(s.2) 7.29(1.2) 7.09(t,l) 4.78(s.2)
Hop chat Ni(pth)2
-
8.72(d,l) 7.53(1,2) 7.l4(m,2) 6,79(m,l) 6,56 va 6,32(s,2)
Pd(pth)2
-
8,70(d,l) 7,58(m.2)*
7,l6(q.2) 6,80(m,l) 7.58(m,l) ;
7,37(s,l) (b)
Hinh 2. Phd ' H - N M R cua Hpth (a) va Ni(pth)2 (b) Trudc bet cd the thdy phd cua phdi tu khac vdi phd cua hai phuc chat vd phd cua 2 phuc chat lai khd gidng nhau. Tdng sd proton trong phdi tir nhieu hon trong hai phiie chdt Id 1.
Dieu dd chimg Id phdc chdt dd dugc tao thdnh vd trong 2 phirc chdt cdc phdi tu deu bi tdch mdt proton de tdn tai dudi dang anion mdt dien lich am. Tin hieu cdng hudng singlet d 9,6 ppm trong phd cua phdi tu dugc gdn cho proton nhdm N ' " ' H khdng thay xudt hien trong phd cua cdc phuc chdt. Dieu ndy chung Id phdi tu bi thiol hod. nguyen lu H ndy chuyen sang S nhung ngay sau dd lai bi tdch ra nhudng chd cho ion kim loai trung ldm nhu ket qud nghien cdu phd IR da chi ra.
Mdt vi tri lien kel liep lbeo giiia phdi tu va ion kim loai trung tdm dd Id nguyen tu N ' " . Khi N ' " tham gia tao lien ket phdi tri vdi ion kim loai ldm cho mat do electron tren N ndy gidm, mat do electron bao quanh H cung gidm keo theo do chuv'en dich hod hgc tdng. Tin
Tdng tich phdn chung hdng 3
.i. 13
5. Pho C-NMR cua phoi tu va phuc chat Phd cdng hirdng lu ' C cua Hpth vd Ni(pth)2 dugc chi ra tren hinh 3. Cdc lin hieu cdng hudng cua phdi tu vd cdc phuc chat dugc Met ke trong bdng 2.
:(a)
\ b) Hinh 3. Phd "C-NMR cua Hpth(a) va Ni(pth)2 (b)
1
Trinh Nggc Chau vd dig Tap chi KHOA HOC & CONG NGHE 83(07): 25-29 Bang 2: Cac tin hieu cdng huong trong phd
'-'C- NMR cua phdi tu va phdc chat Hgp chat
Hpth
Qui ket (ppm) CS C vdng benzen
139.23;
179.34 128,01;
124,05; 123,45
CIS 168.62 Ni(pth)2
142.28;
128,09; 120.0;
117,45 trans 171,11 142,01;
128.21;
120,30; 117.60 167,41
I42,6I;I28.25;
120,34; 117,79 Pd(pth)2
trans 169.06
142,61:
128,16:
120.07; 117,63 So sanh phd cua phdi tir va phd cua phirc chat cho thdy cd su khde nhau rd ret. Sir khac nhau de nhdn thdy nhdt Id Irong phd cua ca hai phuc chdt deu cd lung cap pic vdi sir khac nhau khdng nhieu ve vi tri cung nhu cudng do. Sir xuat hien cua cac cap pic ndy cho phep gia thiet rang ca 2 phirc chdt deu tdn tai d hai dang ddng phdn cis va trans, gidng nhu cdc tdc gid [1] da ket ludn khi nghien ciru cdc phuc chal vudng phdng cua Ni(ll) vdi thiosemicacbazit bang pbuong phdp phd hap thu electron. Vi cdc ddng phdn trans ben hon ddng phdn cis nen trong mdi cap, pic cd cudng do Idn hon la cua dang trans, pic cd cudng do nhd hon la cua dang cis.
Cac lin hieu cdng budng cua cacbon nhdm CS Irong phd cua phuc chdt deu cd do chuyen dich hda hgc giam so vdi phd cua phdi tu tir do: trong phd cua Ni(ptb)2 vd Pd(pth)2 Idn lugt d 171,11 vd 169,06 ppm (dang trans) vd d 168.62 va 167,41 ppm (dang cis). Cd tb^ sau kbi xay ra su thiol hod thi nguyen tu CS tham gia vdo he lien hgp nen mat do electron cd thd bu dap cho viec lao thdnh lien kel vdi kim loai qua S dan den sir thay ddi khdng nhieu cda vi tri cdng budng.
Tin bieu cdng budng cda cdc nguyen lu cacbon trong vdng benzen thay ddi khdng dang ke deu xudt hien trong khodng 117-143 ppm trong phdi tu lu do cung nhu Irong cd dang cis va dang trans cua ca hai phirc chdt.
Nhu vdy. kel qua nghien cuu phd '"C-NMR ngoai viec xdc nhdn cac ket luan khi nghien 28
cuu phd IR vd 'H-NMR v^ lien ket giua phdi tu vd ion kim loai qua nguyen tu S cdn cho phep khang dinh phiic chat tdn tai dudi hai dang cis vd trans.
Tu sir ket qua tat cd cac phan tich tren. chdng tdi dua ra gid thiet ve cdng thirc cdu tao cua 2 phuc chat nhu tren hinh 3.
(^> / ( - l l
/ = ^
ID X /
/ ' \ ( . |
S .NH,
,".7^ Ch!
S NH,
\ / •
/ \ « "
C = N
Os'
v.-\M:Ni. Pd
dang trans dang cis Cciii tgo cua phitc cua Nl(pth)2 vd Pd(plh)2 Hinh 3. Phd "C-NMR cua Hpth(a) va Ni(pth)2 (b)
KET L U A N
Da tdng hgp dugc hai phuc chat cua Ni(II) va Pd(ll) vdi N ' '-phenyl thiosemicacbazit. Phdi tu vd cac phuc chat da dugc nghien cuu bang cdc phuong phdp phdn lich nguyen td, phd khdi lugng, phd hap thu hdng ngoai vd phd cdng hudng tu hat nhdn ' H vd '"'C. Kel qua thu dugc cho phep khdng dinh cdng thuc phan tu va dua ra gid thiet ve cau lao cua phdi td va phuc chal tdng hop dugc.
TAI LIEU THAM KHAO
[I]. A. Sirota and T. Sramko, Square planar Ni"
complexes of Ihiosemicarhazide. Inorganica ChimicaActa. 8, 289-291. 1974.
[2]. CK. S. Pillai, U.S. Nandi and Warren, Levinson, Interaction of DNA with Anti-Cancer Drugs: Copper-Thiosemicarbazide System, Bioinorganic chemistry 7, 151-157, 1977.
[3]. Ebenso. E.E., Ekpe U.J. Effect of molecular structure on the efficiency of amides and thiosemicarbazones used for corrosion inhibition of mild steel in hydrochloric acid. Materials Chemistry and Physics, 60, 79-82, 1999.
[4]. J. Maslowska. Thiosemicarbazidc complexs antimony (III) halides. Polyhedron Vol. 4, No. I, 23-27, 1985.
[5]. Paolo P.. Andrea V. Chemoselective homogeneous hydrogenation of phenylacetylene
Trjnh Nggc Chau va cT/^' Tap chi KHOA HOC & CONG NGHE 83(07): 25 - 29 using thiosemicarbazone and Synthesis. Cytotoxic and Antimalarial Activities thiobenzo>ihydrazone palladium(II) complexes as of Benzoyl Thiosemicarbazone Analogs of catalists. J. Chem. Soc. Dalton Trans., 2715-2721, Isoquinoline and Related Compounds,
1998. Molecules. 15(2), 988-996, 2010.
[6].Ratchanok Pingaew, Supaluk [7] http://www.sisweb.com/mstools/isotope Prachayasittikul and Somsak Ruchirawat,
SUMMARY
SYNTHESIS, STRUCTURAL INVESTIGATION OF COMPLEXES BETWEEN Ni(II) AND Pd(II) WITH N ' " - P H E N Y L T H I O S E M I C A R B A Z I D E
Trinh Ngoc Chau', Nguyen Thi Bich Huong , Hoang Duy Cuong' , Nguyen Thi Thanh
'College of Natural Science. TNU 'College of Education . TNU
The reaction between N'^' - phenyl thiosemicarbazidc (Hpth) and Ni(ll) or Pd(ll) in weak base medium (pH= 9-10) forms two complexes: Ni(pth)2 and Pd(pth)2. They were studied by mean of chemical analytical, infrared. 'H and '-'C nuclear magnetic resonance and mass spectroscopies. The observed data demonstrate that the ligands coordinate to the metal ions via S and N' ' atoms and form the square planar complexes with five-membered rings. The data of 'C-NMR spectra may distinguish the trans or cis configurations of the both complexes
Key words: ihiosemicarhazide, N''"-phenyl thlosemlcarbazide, complex of Nl(ll), complex of Pd(ll), square planar complex
Tel: 01684 9^5 666
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