Nucleophically transformed N-heterocyclic nitriles trapped by cyanooxomolybdates(IV): Crystallographic and spectroscopic study

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• 作者：Anna Ryniewicz ; Monika Tomecka ; Janusz Szklarzewicz ; Dariusz Matoga ; Wojciech Nitek
• 关键词：Molybdenum(IV) ; 2 ; 3-Dicyanopyrazine ; 2-Pyridinecarbonitrile ; Nitrile reactivity ; Crystal structure
• 刊名：Polyhedron
• 出版年：2012
• 出版时间：19 September, 2012
• 年：2012
• 卷：45
• 期：1
• 页码：229-237
• 全文大小：1321 K

文摘

The reaction of K₃Na[Mo(CN)₄O₂]¡¤6H₂O with 2,3-dicyanopyrazine or 2-pyridinecarbonitrile in aqueous media results in isolation of two new compounds of formulae (PPh₄)₂[Mo(CN)₃O(pzac)]¡¤2H₂O (Hpzac = 3-carbamoyl-2-pyrazinecarboxylic acid) and (PPh₄)₂[Mo(CN)₃O(pynccn)]¡¤3H₂O¡¤EtOH (Hpynccn = 2-pyridineiminocarbonitrile) respectively. X-ray single crystal structure measurements as well as physicochemical measurements confirm transformations of 2,3-dicyanopyrazine to 3-carbamoyl-2-pyrazinecarboxylic acid and 2-pyridinecarbonitrile to 2-pyridineiminocarbonitrile. All complexes are characterized by elemental analysis, IR and UV-Vis spectroscopy. Metal-assisted ligand transformations are studied spectrophotometrically in the pH range 8.5-11.5. Two different pathways of nitrile reactivity are shown and discussed.