Synthesis and characterization of tricarbonyl–molybdenum complexes bearing monoaza-trithia-macrocyclic ligands

• Published in: Inorganica Chimica Acta Vol. 401; pp. 101 - 106
• Main Authors: Ogawa, Takahiko, Koike, Koji, Matsumoto, Jun, Kajita, Yuji, Masuda, Hideki
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 24.05.2013
• Subjects: Carbon monoxide; Crystal structure; Hydrogen bond; Macrocycle; Molybdenum; Carbon monoxide; Molybdenum; Macrocycle; Hydrogen bond; Crystal structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2013.03.027

Novel tricarbonyl–molybdenum complexes fac-[Mo(CO)3(L12Py)] (L12Py=N-(2-pyridylmethyl)-1,4,7-trithia-10-azacyclododecane) and fac-[Mo(CO)3(L14H)] (L14H=1,4,7-trithia-11-azacyclotetradecane), have been synthesized by the reaction of [Mo(CO)6] with monoaza-trithia-macrocyclic ligands in toluene. [Display omitted] •We prepared novel molybdenum–tricarbonyl complexes bearing macrocyclic ligands.•Molecular structure of complex has intra- and intermolecular hydrogen bond.•We compare CO stretching vibration of several carbonyl complexes by FT-IR.•Hydrogen bond interaction controls the environment around metal center. Novel tricarbonyl–molybdenum complexes bearing monoaza-trithia-macrocyclic ligands (LXR), [Mo(CO)3(LXR)] (X=12 or 14, R=H), and [Mo(CO)3(L14Py)Mo(CO)4] have been synthesized to gain an understanding of the unique properties of macrocyclic ligands. X-ray structure analysis of [Mo(CO)3(L14H)] has revealed that intra- and intermolecular hydrogen bonds existed and these interaction regulated CO bond lengths. In addition, vibrational spectroscopy indicates that a specific hydrogen bonding interaction affects the strength of the binding of carbon monoxide molecules to the metal. In case of using L14Py, it is expected that dinuclear molybdenum complex was generated.