Malaysian Journal of Analytical Sciences Vol 23 No 5 (2019): 828 - 838

SYNTHESIS OF PALLADIUM(II) DIIMINE COMPLEXES AND THE HYDROLYSIS OF α-DIIMINE LIGAND

(Sintesis Kompleks Diimina Palladium(II) dan Hidrolisis Ligan α-Diimina)

Suzie Hui Chin Kuan¹*, Meng Guan Tay¹, Zhi-Qiang Liu²

¹Faculty of Resource Science and Technology,

Universiti Malaysia Sarawak, 94300 Kota Samarahan, Malaysia

²State Key Lab of Crystal Materials,

Shandong University, 27 Shanda South Road, Jinan, 250100, China

*Corresponding author: suzie_kuan0807@hotmail.com

Received: 23 May 2019; Accepted: 28 August 2019

Abstract

The reactions of dichlorobis(acetonitrile)palladium(II) precursors with 1,4-diaza-1,3-butadienes (α-diimine) give rise to the products (1,4-bis(4-methoxyphenyl)-1,4-diaza-1,3-butadiene)dichloropalladium(II) (2a) and (1,4-bis(4-methylphenyl)-1,4-diaza-1,3-butadiene)dichloropalladium(II) (2b), as deduced from elemental analysis, FTIR, and UV-Vis. Both complexes are soluble in dimethylformamide and single crystals were collected for an X-ray crystallographic study. Based on the crystallographic data, complex 2a is crystalized in a monoclinic system with P2₁/c space group. The Pd-N bond lengths for Pd01-N004 and Pd01-N005 are 2.045(2) and 2.033(2) Å, respectively. Surprisingly, when complex 2b dissolved in dimethylformamide, 4-methylaniline was produced from the hydrolysis of the α-diimine ligand 1b, therefore trans-dichloridobis(4-methylaniline-κN)-palladium(II) (2c) was formed as confirmed, by crystallographic data. Complex 2c is crystallized in a triclinic system with P 2₁/b 2₁/c 2₁/a (Pbca) space group. The bond lengths of Pd-N are 2.050(3) Å and Pd-Cl is 2.318(8) Å. There are weak intermolecular N-H···Cl hydrogen bonds, that are responsible for the packing of the molecules in formation.

Keywords: 1,4-diaza-1,3-butadienes, palladium diimine complex, X-ray crystal, hydrolysis, hydrogen bonds

Abstrak

Tindak balas diklorobis(asetonitril)palladium(II) prakursor dengan 1,4-diaza-1,3-butadiena menghasilkan produk sebagai (1,4-bis(4-metoksifenil)-1,4-diaza-1,3-butadiena)dikloropalladium(II) atau 4-bis(4-metilfenil)-1,4-diaza-1,3-butadiena)dikloro palladium(II) yang disimpulkan daripada analisis unsur, FTIR, dan UV-Vis. Kedua-dua kompleks ini larut dalam dimetilformamida dan hablur tunggal telah dikumpulkan untuk kajian kristalografi sinar-X. Berdasarkan data kristalografi, kompleks 2a menghablur dalam sistem monoklinik dengan kumpulan ruang P21/c. Panjang ikatan Pd-N ialah 2.045 (2) untuk Pd01-N004 dan 2.033 (2) Å untuk Pd01-N005. Walau bagaimanapun, apabila kompleks 2b larut dalam dimetilformamida, 4-metilanilina telah dihasilkan dari hidrolisis ligan α-diimine 1b, oleh itu, trans-dikloroidobis(4-metilanilina-κN)-palladium(II) (2c) telah terbentuk seperti yang dibuktikan oleh data hablur. Kompleks 2c menghablur dalam sistem triklinik dengan kumpulan ruang P 21/b 21/c 21/a (Pbca). Panjang ikatan Pd-N ialah 2.050 (3) Å dan Pd-Cl ialah 2.318 (8) Å. Terdapat ikatan intermolekul yang lemah N-H···Cl yang bertanggungjawab untuk pemadatan molekul.

Kata kunci:  1,4-diaza-1,3-butadiena, kompleks diimina palladium, hablur sinar-X, hidrolisis, ikatan hidrogen

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