Discovering the chemical reactivity of the molecular oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)]

The ability of the oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)] (1) to act as an organometallic ligand has been studied from both theoretical and experimental points of view. DFT calculations have allowed understanding the electronic structure of 1, and rationalizing its chemical behavior by comparison with the electronic structures of isoelectronic species [{Ti(η5-C5Me5)(μ-O)}3(μ3-CH)] and [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]. Reactions of 1 with different inorganic molecules such as [Mo(CO)3(1,3,5-Me3C6H3)] or AlEt3 have confirmed the possibility of 1 to act as a tridentate or monodentate ligand to give the [{(CO)3Mo}(μ3-O)3{Ti3(η5-C5Me5)3(μ3-N)}] (2) and [{Et3Al}(μ3-O){(μ-O)2Ti3(η5-C5Me5)3(μ3-N)}] (3) complexes, respectively. Surprisingly, reactions of 1 with [M(CO)6] (M = Cr, Mo, W) complexes led to activate the μ3-N unit in 1 to afford the new compounds [Ti3(η5-C5Me5)3(μ-O)4{(NC)M(CO)5}]2 [M = Cr (4), Mo (5), W (6)]. Molecular structures of complexes 2–6 have been established by single crystal X-ray analysis.