Malaysian
Journal of Analytical Sciences Vol 19 No 3 (2015): 520 530
SYNTHESIS,
STRUCTURAL AND SPECTROSCOPIC STUDIES OF PALLADIUM(II) METALLO-MACROCYLES
CONTAINING ANCILLARY BLOCKING LIGANDS AND N,N-2,6-BIS(3-PYRIDYLMETHYL)PYRIDINE
DICARBOXAMIDE
(Sintesis,
Struktur Dan Kajian Spektroskopik Makrosiklik-Berlogam Paladium(II) Terkandung
Ligan Sampingan dan 2,6-Bis(3-Piridilmetil)Piridin
Dikarbosamida)
Maisara Abdul Kadir 1*, Rafidah Ramli 1,
Nursyazwani Kassim1, Nafisah Mansor1, Christopher James
Sumby 2
1School of Fundamental Science,
Universiti
Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia.
2 School of Chemistry & Physics,
The University
of Adelaide, 5005 Adelaide, Australia
*Corresponding author: maisara@umt.edu.my
Received: 22
March 2015; Accepted: 18 May 2015
Abstract
Reaction between
N,N-2,6-bis(3-pyridylmethyl)pyridine dicarboxamide (L) with dichloropalladium(II) 2,2-bipyridine [PdCl2(2,2-bipy)]
and dichloropalladium(II) ethylenediamine [PdCl2(en)] gave rise to
two novel metallo-macrocycles, [Pd(L)(2,2-bipy)](PF6)2
(A1) and [Pd(en)(L)](PF6)2·H2O·2CH3OH
(A2), respectively. These complexes were characterized by
spectroscopic techniques such as Fourier Transform
Infrared (FT-IR), Nuclear Magnetic Resonance (NMR), electrospray
ionization mass spectrometry (ESI-MS) and elemental analysis. The studies on
the interactions between the protons of the ligand and the protons of the
ancillary ligands (etc. bipy, en) of the complexes were identified by using two dimensional NMR techniques such as Nuclear Overhauser Spectroscopy (2D NOESY) and correlation
spectroscopy (COSY). X-ray crystallography shows that complex A2 form a bowl-like structure with one
hexafluorophosphate anions encapsulated in the molecule cavity. The hexafluorophosphate anions form weak
interaction with the ancillary ligand ethylenediamine (N-H
F, d = 2.379, D = 3.113 Ε) which stabilized by weak C-HΌF hydrogen
bonding. The presence of weak anion-p contact is also
observed between the anion and the central pyridine of the metallo-macrocycle.
Further analysis by diffusion-ordered spectroscopy (DOSY)
has shown that the diffusion rates of complexes A1 and A2 are lower from
the theoretical value. This might be due to the complexing of
hexafluorophosphate anions that increase the hydrodynamic radii of the
complexes.
Keywords: flexible, anion-p, hydrogen
bonding, palladium, metallo-macrocycles
Abstrak
Tindak balas
antara ligan 2,6-bis(3-piridilmetil)piridin
dikarbosamida (L) dengan
dikloropaladium(II) 2,2-bipiridin[PdCl2(2,2-bipy)] dan
dikloropaladium(II) etilenadiamina [PdCl2(en)] telah memberikan dua
makrosiklik- berlogam yang baru, masing-masing sebagai [Pd(L)(2,2-bipy)](PF6)2 (A1) dan [Pd(en)(L)](PF6)2·H2O·2CH3OH
(A2). Kompleks ini telah dicirikan dengan kaedah spektroskopi
seperti Fourier Pengubah Inframerah (FT-IR), Nukleus Magnetik
Resonan (NMR), elektrosemburan pengionan spektrometri jisim (ESI-MS) and analisis
unsur. Kajian interaksi antara proton terhadap ligan serta proton terhadap
ligan sampingan (seperti bipy, en) dalam kompleks dikenalpasti dengan
menggunakan teknik NMR dua dimensi seperti spektroskopi Nuklear
Overhauser (2D NOESY) and spektroskopi Korelasi
(COSY). Kajian X-ray kristalografi menunjukkan bahawa kompleks A2 membentuk struktur mangkuk dengan
satu anion heksafluorofosfat terperangkap dalam kaviti molekul. Anion heksafluorofosfat
membentuk ikatan lemah dengan ko-ligan etilenadiamina (N-H
F, d = 2.379, D = 3.113 Ε) dan distabilkan oleh ikatan hidrogen C-HΌF. Kehadiran
ikatan lemah anion-p juga dilihat di antara anion
dengan pusat piridin makrosiklik-berlogam itu. Analisis seterusnya menggunakan
spektroskopi sebaran turutan (DOSY) menunjukkan kadar sebaran yang rendah oleh A1 dan A2 berbanding nilai teori. Ini mungkin disebabkan oleh
pengkompleksan anion heksafluorofosfat yang meningkatkan jejari hidrodinamik
kompleks tersebut.
Kata
kunci: ligan,
ikatan anion-p, ikatan hidrogen, palladium,
makrosiklik-berlogam
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