Sains Malaysiana 47(9)(2018): 2083–2090

http://dx.doi.org/10.17576/jsm-2018-4709-16

 

Synthesis and X-Ray Single Crystal Study of 5-(4,4,5,5 – Tetramethyl – 1,3,2 –Dioxoborolane) – 10,20 – Diphenylporphyrin

(Sintesis dan Kajian Sinar-X Hablur Tunggal 5-(4,4,5,5-tetrametil- 1,3,2-dioxoborolana)-10,20-difenilporfirin)

 

NUUR HAZIQAH MOHD RADZUAN¹, NAWWAR HANUN ABDUL MALEK¹, MOHAMMAD FADZLEY NGATIMAN², TAN KE XIN³, MOHD BAKRI BAKAR³, NURUL IZZATY HASSAN¹

& MUNTAZ ABU BAKAR^1*

 

¹School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

²Centre for Research and Instrumentation Management, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

³Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor, Johor Bahru, Johor Darul Takzim, Malaysia

 

Received: 30 March 2018/Accepted: 17 May 2018

 

 

ABSTRACT

Borylated porphyrin is one of building blocks in coupling reactions to obtain the multiporphyrin containing two, three or more subunits of porphyrins. In this study, one of borylated porphyrin derivatives, 5-(4,4,5,5 – tetramethyl – 1,3,2 – dioxoborolane) -10,20 – diphenylporphyrin (B-DPP) was synthesized through four steps of reactions. The building block of porphyrin, dipyrromethane was synthesized through a condensation reaction in the presence of trifluoroacetic acid as catalyst. Subsequently, A2B2 type of porphyrin was obtained by Lindsey condensation reaction followed by bromination reaction to produce porphyrin halide. Suzuki cross coupling reaction between porphyrin halide and pinacolborane with Pd (II) catalyst afforded 40% of borylayed porphyrin. The product was successfully characterized by using nuclear magnetic resonance spectroscopy (NMR) and UV-Visible spectroscopy (UV-Vis). This compound crystallized from a mixture of dichloromethane/methanol to give violet needle-like crystal. Crystallographic studies showed this compound crystallized in monoclinic system with space group of P2₁/c.

 

Keywords: Borylated porphyrin; porphyrin; Suzuki cross coupling; X-ray structural study

 

ABSTRAK

Sebatian porfirin borilasi merupakan salah satu blok binaan dalam tindak balas penggandingan untuk mendapatkan sebatian multiporfirin yang terdiri daripada dua, tiga atau lebih unit porfirin. Melalui kajian ini, salah satu terbitan sebatian porfirin borilasi, 5-(4,4,5,5-tetrametil-1,3,2-dioxoborolana)-10,20-difenilporfirin (B-DPP) telah disintesis melalui empat langkah tindak balas. Blok binaan asas iaitu dipirometana disintesis melalui tindak balas penyejatan dengan kehadiran asid trifloroasetik, selaku mangkin. Porfirin jenis A2B2 diperoleh melalui tindak balas penyejatan Lindsey dan diikuti dengan tindak balas pembrominan untuk menghasilkan sebatian porfirin halida. Tindak balas penggandingan Suzuki antara sebatian porfirin halida dan pinakolborona menggunakan bahan pemangkin Pd (II) menghasilkan 40% sebatian porfirin borilasi. Sebatian ini telah berjaya dicirikan dengan menggunakan teknik resonans magnetik nuklear (RMN) dan spektroskopi ultra-lembayung boleh nampak (UL-BN). Sebatian ini menghablur daripada sistem campuran pelarut diklorometana/methanol dan menghasilkan kristal jejarum berwarna ungu. Kajian kristalografi menunjukkan sebatian ini terhablur dalam sistem monoklinik dengan kumpulan ruang P2₁/c.

 

Kata kunci: Kajian struktur sinar-X; porfirin; porfirin borilasi; tindak balas penggandingan Suzuki

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*Corresponding author; email: muntaz@ukm.edu.my