New O‐centered titanium chalcohalide: synthesis and structure of Ti 4 O(Se 2 ) 4 Br 6

New O‐centered tetranuclear titanium complex Ti 4 O(Se 2 ) 4 Br 6 has been prepared from TiSe 1.73 , Se, SeO 2 and Br 2 at moderate temperature by ampule synthesis. Its X‐ray crystal structure (monoclinic space group P 2 1 / c, a= 9.4850(2), b =11.4667(2), c =19.1413(5)Å, β =92.0080(10)°, Z =4, V =2080.56(8)Å 3 ) includes molecular complex Ti 4 O(Se 2 ) 4 Br 6 based on fragment {Ti 4 (μ 4 ‐O)} coordinated by diselenide (Se 2 ) 2− and bromide bridging ligands. Ti 4 O(Se 2 ) 4 Br 6 is a new member of family of O‐centered tetranuclear complexes with the fragment { M 4 (μ 4 ‐O)( Q 2 ) 4 } ( M =Ti, Nb, Ta; Q =S, Se, Te); here we discuss its synthetic features, crystal and electronic structure.