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Sains Malaysiana 47(8)(2018): 1775–1785 http://dx.doi.org/10.17576/jsm-2018-4708-16
Synthesis, Structure and Spectroscopic
Properties of Oxovanadium Tris(3,5-dimethylpyrazolyl)borate Aroylthiourea
Complexes
(Sintesis, Struktur dan Sifat Spektroskopi Kompleks
Oksovanadium Tris(3,5-dwimetilpirazolil)borat Aroiltiourea)
SYAHIDAH MOHD TAHIR1, AISHA AL-ABBASI1, QURNISHA GHAZALI1, KHUZAIMAH ARIFIN2 & MOHAMMAD B. KASSIM1,2*
1School of Chemical Sciences and Food
Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600
UKM Bangi, Selangor Darul Ehsan, Malaysia
2Fuel Cell Institute, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia
Diserahkan: 21 September 2017/Diterima: 4
Mac 2018
ABSTRACT
Aroylthiourea ligands, 1-aroyl-3-cyclohexyl-3-methylthiourea (HL1),
1-(2-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL2),
1-(3-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL3)
and 1-(4-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL4) were
synthesized through a condensation reaction of methylcyclohexylamine
and aroylisothiocyanate with a general formula (X-Ph)(CO)NH(CS)N(C6H5)(CH3) where X = H, o-Cl, m-Cl and p-Cl, fully characterized
by CHNS micro
elemental analysis, infrared spectroscopy, UV-visible, nuclear magnetic
resonance (1H, 13C) and X-ray crystallography.
1-(3-chloroaroyl)-3-cyclohexyl-3-methylthiourea (HL3)
crystallized in the monoclinic system, a=14.504(3), b=4.9599(11),
c=22.325(5) Å, β=98.461(7)°, Z= 4 and V=1588.5(6)
Å with space group P21/c. The IR spectra of the
ligands exhibits the characteristic v(CO) and v(N-H) at range 1701-1640
cm-1and 3317-3144 cm-1, respectively. Whereas
the 1H and 13C NMR spectra shows the resonances
for N-H and -CO groups at range 8.3-8.5 and 160-163 ppm, respectively.
A one-pot reaction involving the aroylthiourea ligand, oxovanadium(IV)
ion and potassium hydrotris(3,5-dimethylpyrazolyl)borate (KTp*)
complex gave the desired [oxovanadium(IV)(tris(pyrazolyl)borate)(aroylthiourea)]
complexes namely Tp*VOL1,
Tp*VOL2, Tp*VOL3
and Tp*VOL4 and all complexes were characterized
accordingly. X-ray study showed that Tp*VOL1 adopted
a monoclinic crystal, a=3.415(2), b=19.463(3), c=14.22(3) Å,
β=107.411(4)°, Z= 4 and V=3542.7(11) Å with P21/c space
group. The VO2+ center
adopted a pseudo-octahedral geometry O2N3S,
with the oxovanadium(IV) coordinated to the bidentate ligand (X-Ph)(CO)NH(CS)N(C6H5)(CH3)
and tridentate Tp* ligands. The results showed that aroylthiourea
ligands behave as bidentate chelate through O and S atom and the
Tp* C3v symmetry adds stabilization to the VO2+ through
its protective tripodal geometry.
Keywords: Aroylthiourea; chelate;
oxovanadium(IV); tris(pyrazolyl)borate; vanadyl
ABSTRAK
Ligan aroiltiourea, 1-aroil-3-sikloheksil-3-metiltiourea (HL1),
1-(2-kloroaroil)-3- sikloheksil-3-metiltiourea (HL2),
1-(3-kloroaroil)-3- sikloheksil-3-metiltiourea (HL3) dan
1-(4-kloroaroil)-3-sikloheksil-3-metiltiourea (HL4)
telah disintesis melalui tindak balas kondensasi antara metilsikloheksilamina
dan aroilisotiosianat dengan formula asas, (X-Ph)(CO)NH(CS)N(C6H5)(CH3
dengan X=H, o-Cl, m-Cl dan p-Cl. Pencirian penuh telah
dilakukan dengan mikroanalisis unsur CHNS, spektroskopi inframerah, ultralembayung boleh nampak,
resonans magnet nukleus (1H, 13C) serta kristalografi
sinar-X. Ligan, 1-(3-kloroaroil)-3-sikloheksil-3-metiltiourea (HL3)
menghablur dalam sistem monoklinik, a=14.504(3), b=4.9599(11), c=22.325(5)
Å, β=98.461(7)°, Z= 4 dan V=1588.5(6) dengan kumpulan
ruang P21/c.
Spektrum IR bagi kesemua ligan mempamerkan sifat v(CO) dan v(N-H)
masing-masing dalam lingkungan 1680-1690 cm-1 dan 3120-3144
cm-1. RMN 1H dan 13C menunjukkan resonans bagi
kumpulan (N-H) dan –CO masing-masing dalam lingkungan 8.3-8.5
dan 160-163 ppm. Tindak balas serentak melibatkan ligan aroiltiourea,
ion oksovanadium(IV) dan kompleks kalium hidrotris(3,5-dimethilpirazolil)borat
(KTp*) untuk membentuk kompleks yang diinginkan [oksovanadium(IV)(tris(pirazolil)borat)(aroiltiourea)]
dinamakan Tp*VOL1,
Tp*VOL2, Tp*VOL3
dan Tp*VOL4 telah berjaya disintesis dan
dicirikan. Kristalografi sinar-X menunjukkan Tp*VOL1 mempunyai
sistem hablur monoklinik, a=3.415(2), b=19.463(3), c=14.22(3) Å,
β=107.411(4)°, Z= 4 dan V=3542.7(11) Å dengan kumpulan
ruang P21/c.
Pusat VO2+ menyarankan geometri kompleks
yang terbentuk adalah pseudo-oktahedral O2N3S
dengan pusat oksovanadium(IV) berkoordinat dengan ligan bidentate
(X-Ph)(CO)NH(CS)N(C6H5)(CH3)
dan ligan tridentat Tp*. Ligan aroiltiourea bertindak sebagai pengkelat
bidentat melalui atom O dan S dan ligan Tp* yang bersimetri C3v
memberikan kestabilan kepada pusat VO2+ dengan
geometri tripodal.
Kata
kunci: Aroiltiourea; kelat; oksovanadium(IV); tris(pirazolil)borat; vanadil
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*Pengarang untuk surat-menyurat, email: mb_kassim@ukm.edu.my
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