Synthesis, Structure, and Reactivity of Molybdenum– and Tungsten–Indane Complexes with Trisborate Ligand

• Published in: Molecules (Basel, Switzerland) Vol. 29; no. 4
• Main Authors: Itazaki, Masumi, Nouichi, Kunihisa, Ookuma, Ken-ichiro, Moriuchi, Toshiyuki, Nakazawa, Hiroshi
• Format: Journal Article
• Language: English
• Published: MDPI AG 01.02.2024
• Subjects: Borates; Molybdenum; Tungsten
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules29040757

The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (Et[sub.4]N[TpMo(CO)[sub.3]] and Et[sub.4]N[Tp*Mo(CO)[sub.3]] (Tp = hydridotris(pyrazolyl)borate, Tp* = hydridotris(3,5-dimethylpyrazolyl)borate)) and InBr[sub.3] at a 1:1 molar ratio afforded molybdenum–indane complexes (Et[sub.4]N[TpMo(CO)[sub.3](InBr[sub.3])] 1 and Et[sub.4]N[Tp*Mo(CO)[sub.3](InBr[sub.3])] 2). In addition, tungsten–indane complexes, Et[sub.4]N[TpW(CO)[sub.3](InBr[sub.3])] 3 and Et[sub.4]N[Tp*W(CO)[sub.3](InBr[sub.3])] 4, were obtained by the reaction of corresponding tungsten complexes. Complex 4 reacted with H[sub.2]O to form the hydrido complex Tp*W(CO)[sub.3]H, in which the W–In bond was cleaved. On the other hand, 4 reacted with three equiv. of AgNO[sub.3] to form Et[sub.4]N[Tp*W(CO)[sub.3]{In(ONO[sub.2])}] 5, in which three substituents on the In were exchanged while retaining the W–In dative bond. Complexes 1–5 were fully characterized using NMR measurements and elemental analyses, and the structures of 1–5 and Et[sub.4]N[Tp*W(CO)[sub.3]] were determined via X-ray crystallography. These are the first examples of mononuclear molybdenum– and tungsten–indane complexes with Mo–In and W–In dative bonds.