Photo-substitution reactions of some transition metal organometallics and their spectroscopic characterizations

Abstract

Bu çalışmada tiyosemikarbazit ligandının, VIB ve VIIB grubu metal karbonil [metal hegzakarbonil (Metal=Krom; 1, Molibden; 2, Wolfram; 3); Bromo pentakarbonilrenyum(I) ; siklopentadienil trikarbonilmangan(I) kompleksleri ile fotokimyasal tepkimeleri sonucunda bir seri orjinal karbonil kompleksleri; cis-[metal tetrakarbonil(dihapto-N,S-Tiyosemikarbazit)] (Metal= krom; 1, Molibden; 2, Wolfram; 3); facical-[brom trikarbonil Renyum(I)-(dihapto-N,N-tiyosemikarbazit)], 4 ve [siklopentadienil monokarbonil Mangan(I)(dihapto-N,N-tiyosemikarbazit)],5 sentezlendi. Sentezlenen komplekslerin yapıları, elemental analiz, FTIR, 1H NMR ve LC-Mass spektrometri yöntemleri ile aydınlatıldı. Spektroskopik bulgulara dayanarak, VIB grubu metal karbonil komplekslerinde (1-3), tiyosemikarbazit ligandının kükürt ve terminal amin azot atomundan bidentat olarak koordine olmasına rağmen, VIIB grubu metal karbonil komplekslerinde (4-5), ligandın terminal amin ve tiyoamid azot atomlarında bidentat olarak koordine olduğu açıklanmıştır. A series of metal carbonyl complexes of VI B and VII B groups having the general compositions cis[metal tetracarbonyl-(dihapto-N,S-thiosemicarbazide)], [Metal= Chromium; 1, Molybdenum; 2, Wolfram; 3] and facial-[bromine Rhenium(I) tricarbonyl bromine -(dihapto-N,N-thiosemicarbazide)], 4 and [Manganese(I) monocarbonyl cyclopentadienyl-(dihapto-N,N-thiosemicarbazide)], 5 with thiosemicarbazide (TSC) have been prepared and characterized by elemental analysis, LC-mass spectrometry, FTIR and 1H NMR spectroscopy. The spectral data suggest the involvement of sulfur and terminal amino nitrogen of TSC in coordination to the central metal ion for VI B metal carbonyl complexes whereas the terminal amino nitrogen and thioamide nitrogen of TSC in coordination to the central metal ion for VII B metal carbonyl complexes. On the basis of spectral studies, an octahedral geometry has been assigned for all of the complexes.