Elvan ÜSTÜN, Cemal KAYA

Cs Simetrisindeki Trikarbonil Komplekslerinin Kuvvet Sabitlerinin Yeni Bir Metot ile Analizi

Erken dönem çalışmalarında genellikle katalizör olarak kullanılan metal karbonil kompleksleri, CMIA ve CORMs olarak potansiyel farmakolojik uygulamalarda kullanıldıkları için son zamanlarda daha fazla dikkat çekmektedirler. Ayrıca metal karboniller, orta-IR bölgesindeki özel spektroskopik özellikleri sayesinde biyoprob ve protein etiketleme ajanı olarak kullanılmaktadır. Karbonil komplekslerinin IR bandlarının sayısı ve yeri, karbonil ve diğer bağlı ligandların oluşturduğu kimyasal çevreden etkilenmektedir. Metal karbonil komplekslerinin kuvvet sabitleri, bağlı ligandların elektronik etkileri konusunda kalitatif ve kantitatif olarak anlamlı bilgiler verebilirler. Bununla birlikte, kuvvet sabitleri, karbonil komplekslerinin izolobal benzerliği ile ilgili kullanışlı bir kriter olarak değerlendirilebilir. Bu çalışmada önerilen yeni ve basit metot ile farklı ikincil ligandlar bulunduran pek çok metal karbonil kompleksinin kuvvet ve etkileşim sabitleri, bu ligandların σ-verici/π-alıcı özellikleri hakkında öngörü oluşturmak için hesaplanmıştır.

Anahtar Kelimeler:

Metal karbonil kompleksleri, CO-ayrımlı kuvvet alanları, Kuvvet sabitleri

A New Method for Analyzing the Force Constants of Tricarbonyl Complexes with CS Symmetry

Metal carbonyl complexes that generally used as catalyst in early researches have attracted much attention recently due to their potential pharmaceutical applications as CMIA and CORMs. Metal carbonyls also have used also as bioprobe, protein-labelling agent thanks to unique spectroscopic feature in mid-IR. The position and the number of carbonyl IR bands have affected by chemical environment of carbonyl unit and coordinated ligands. Therefore, the force constants of metal carbonyl complexes could give meaningful qualitative and quantitative information about the electronic influences of the coordinated ligands. Additionally the force constants could be useful criteria when the carbonyl ligands have evaluated in terms of isolobal analogy. In this study, the stretching and the interaction force constants of many metal carbonyl complexes with lots of different seconder ligands have calculated with a new suggested simple method to gain insight into the σ-donor/π-acceptor properties of these coordinated ligands.

Keywords:

Metal carbonyl complexes, CO-factored force fields, Force constants,

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1. Applegate J C, Okeowo M K, Erickson N R, Neal B M, Berrie C L, Gerasimchuk N M & Barybin M V (2016). First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111). Chemical Science. :1–8.
2. Bour P, Kubelka J & Keiderling T A (2000). Simulations of oligopeptide vibrational CD: Effects of isotopic labeling. Biopolymers 53:380–395.
3. Braterman P S, Harrill R W & Kaesz H D (1964). Spectroscopic Studies of Isotopically Substituted Metal Carbonyls. Journal of the American Chemical Society 2734(50):2851–2855.
4. Brimm E O, Lynch M A & Sesny W J (1954). Preparation and Properties of Manganese Carbonyl. Journal of the American Chemical Society 76(6):3831–3835.
5. Carpenter A E, Mokhtarzadeh C C, Ripatti D S, Havrylyuk I, Kamezawa R, Moore C E, Rheingold A L & Figueroa J S (2015). Comparative measure of the electronic influence of highly substituted aryl isocyanides. Inorganic Chemistry 54(6):2936–2944.
6. Fish R H & Jaouen G (2003). Bioorganometallic chemistry: Structural diversity of organometallic complexes with bioligands and molecular recognition studies of several supramolecular hosts with biomolecules, alkali-metal ions, and organometallic pharmaceuticals. Organometallics 22(d):2166–2177.
7. Ghaffar T, Adams H, Maitlis P M, Sunley G J, Baker M J & Haynes A (1998). Spectroscopic identification and reactivity of [Ir(CO)3I2Me], a key reactive intermediate in iridium catalysed methanol carbonylation. Chemical Communications 2:1023–1024.
8. Gorfti A, Salmain M, Jaouen G, McGlinchey J, Bennouna A & Mousser A (1996). Covalent and selective labeling of proteins with heavy metals. Synthesis, X-ray structure, and reactivity studies of N-succinimidyl and N-sulfosuccinimidyl ester organotungsten complexes. Organometallics 15(10):142–151.
9. Hillard E A & Jaouen G (2011). Bioorganometallics: Future trends in drug discovery, analytical chemistry, and catalysis. Organometallics 30(5):20–27.
10. Kaya C, Karakaş D & Üstün E (2007). A new approach to predicting the carbonyl stretching frequencies of Co2(CO)8 with D3d symmetry. Indian Journal of Chemistry 46A:1388–1392.
11. Kendall A J, Zakharov L N & Tyler D R (2016). Steric and Electronic Influences of Buchwald-Type Alkyl-JohnPhos Ligands. Inorganic Chemistry 55(6):3079–3090.
12. Knör G & Monkowius U (2011). Photosensitization and photocatalysis in bioinorganic, bio-organometallic and biomimetic systems. Inorganic Photochemistry 63:235-289.
13. Morisaki Y, Chen H & Chujo Y (2004). Synthesis and characterization of organometallic conjugated polymers containing tricarbonyl(arene)chromium unit and platinum. Journal of Organometallic Chemistry 689:2684–2689.
14. Motterlini R, Clark J E, Foresti R, Sarathchandra P, Mann B E & Green C J (2002). Carbon monoxide-releasing molecules: characterization of biochemical and vascular activities. Circulation Research 90:E17–E24.
15. Mula B, Beaumont A J, Doyle K O, Gallagher M L & Rooney A D (1999). Charge Transfer Complexes of Arebe-molybdenum-tricarbonyl as heterogenous metathesis catalysts for the polymerization of Phenylacetylene. Journal of Molecular Catalysis 148:23–28. 16. Salmain M, Vessiere A, Varenne A, Brossier P & Jaouen G (1999). A new application of bioorganometallics: the first simultaneous triple assay by the carbonylmetalloimmunoassay (CMIA) method. Journal of Organometallic Chemistry 589:92–97.
17. Schatzschneider U (2014). Novel lead structures and activation mechanisms for CO-releasing molecules (CORMs). British journal of Pharmacology 172:1638-1650.
18. Üstün E, Özgür A, Coşkun K A, Düşünceli S D, Özdemir İ & Tutar Y (2017). Anticancer activities of manganese-based photoactivatable CO-releasing complexes (PhotoCORMs) with benzimidazole derivative ligands. Transition Metal Chemistry 42(4):331–337.
19. Üstün E, Ayvaz M Ç, Çelebi M S, Aşcı G, Demir S & Özdemir İ (2016). Structure, CO-releasing property, electrochemistry, DFT calculation, and antioxidant activity of benzimidazole derivative substituted [Mn(CO)3(bpy)L]PF6 type novel manganese complexes. Inorganica Chimica Acta 450:182–189.
20. Üstün E & Kaya C (2010). Calculating the CO-factored force constants of tricarbonyl complexes with Cs symmetry. Journal of Organometallic Chemistry 695(19–20):2273–2276.