Synthesis, Spectroscopic Investigations, Thermal Analysis and DFT Calculations of Some Pentacarbonyl(Mercaptopyrimidine) Metal(0) Complexes of Group VI B Elements

Year 2022, Volume: 8 Issue: 2, 107 - 115, 26.12.2022

Özlem Ünlü , İzzet Amour Morkan

https://doi.org/10.55385/kastamonujes.1159789

Abstract

Pentacarbonyl-N-mercaptopyrimidinemetal(0) complexes of VIB metals (M: Cr, Mo, W) were formed when hexacarbonylmetal(0) complexes are treated photochemically with 4,6-dimethyl-2-mercaptopyrimidine at 10 ºC. The reported organometallic complexes were purified and isolated under an inert atmosphere. All M(CO)5L complexes were characterized in solution by FTIR-, 1H- and 13C-NMR spectroscopies. The FTIR spectroscopy results showed three absorption bands in the carbonyl region which indicates that the pentacarbonyl metal unit of the complexes has a local C4v symmetry. The 1H- and 13C-NMR spectroscopies showed that the mercaptopyrimidine ligand bonded to the metal complex through the mercaptopyrimidine-nitrogen atom symmetrically. The 13C-NMR spectroscopy results also showed a 1:4 ratio of two peaks in the CO-region, the ratio of the peaks proved the C4v symmetry of these complexes. The thermal behavior of these organometallic complexes is investigated by using DTA/TGA methods. The results of thermal analyses showed that the complexes decomposed at three different temperatures. The density functional theory (DFT) calculations were computed in B3PW91 formalism by Gaussian03W Software. The comparison of the experimental data with the theoretical values showed that the results obtained are compatible with each other. Thus, the accuracy of the experimentally given structural proposal of the obtained organometallic complex compounds was also confirmed through theoretical calculations.

Keywords

Mercaptopyrimidine, Photochemical synthesis, Metal carbonyls, Thermal analysis, DFT.

Supporting Institution

There is no financial support and commercial support.

VI B Grubu Elementlerinin Pentakarbonil(Merkaptopirimidin)Metal(0) Komplekslerinin Sentezi, Spektroskopik İncelemeleri, Termal Analizi ve DFT Hesapları

Abstract

VIB metallerinin (M: Cr, Mo, W) pentakarbonil-N-merkaptopirimidinmetal(0) kompleksleri, hekzakarbonilmetal(0) kompleksleri 10 ºC'de 4,6-dimetil-2-merkaptopirimidin ligandı ile fotokimyasal olarak sentezlendi. Bildirilen organometalik kompleksler, inert atmosfer altında saflaştırılırılarak ve izole edili. Tüm M(CO)5L kompleksleri çözelti içinde FTIR-, 1H- ve 13C-NMR spektroskopileri ile karakterize edildi. FTIR spektroskopi sonuçları, karbonil bölgesinde, komplekslerin pentakarbonil metal biriminin yerel bir C4v simetrisine sahip olduğunu gösteren üç absorpsiyon bandı gösterdi. 1H- ve 13C-NMR spektroskopileri merkaptopirimidin ligandının, merkaptopirimidin-azot atomu yoluyla metal kompleksine simetrik olarak bağlandığını gösterdi. 13C-NMR spektroskopi sonuçları ayrıca CO-bölgesinde 1:4'lük bir oran gösterdi, bu oran komplekslerin C4v simetrisini kanıtladı. Bu organometalik komplekslerin termal davranışı DTA/TGA yöntemleri kullanılarak araştırılmıştır. Termal analizlerin sonuçları, komplekslerin üç farklı sıcaklıkta bozunduğunu göstermiştir. Yoğunluk fonksiyonel teorisi (DFT) hesaplamaları Gaussian03W Software ile B3PW91 formalizmi kullanılırak yapıldı. Deneysel çalışmaların verileri teorik değerlerle karşılaştırıldığında elde edilen sonuçların birbiri ile uyumlu olduğu görülmüştür. Böylece elde edilen organometalik kompleks bileşikleri için deneysel olarak verilen yapısal önermenin doğruluğu teorik olarak da desteklenmiştir.

Keywords

Merkaptopirimidin, Fotokimyasal sentez, Metal karboniller, Termal analiz, DFT.

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