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Halides of Titanium in Lower Oxidation States
Author(s) -
Meyer Gerd,
Gloger Thomas,
Beekhuizen Jan
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900086
Subject(s) - octahedron , halide , crystallography , titanium , chemistry , ternary operation , crystal structure , pentagonal bipyramidal molecular geometry , cluster (spacecraft) , inorganic chemistry , organic chemistry , computer science , programming language
New investigations on the di‐ and trihalides of titanium, TiX 2 and TiX 3 (X = Cl, Br, I), with their 3d 2 and 3d 1 electronic configurations, confirm the early observations and conclusions of Klemm. At sufficiently low temperatures, Ti–Ti single bonds are formed in the one‐dimensional trihalides, i.e., Ti–Ti dimers are observed. Equally, in the two‐dimensional dihalides, {Ti 3 } triangles occur with three single bonds. Phase transitions were detected from single‐crystal or powder X‐ray diffraction data, from magnetic measurements and thermal analysis. Except for the binary halides a number of ternary halides ATiX 3 (extended chains of facesharing octahedra), K 4 Ti 3 Br 12 (triples of face‐sharing octahedra), Na 2 Ti 3 Cl 8 (triangular trimers), A 3 Ti 2 X 9 (dimers of face‐sharing octahedra), and A 3 TiX 6 (isolated octahedra) as well as the mixed‐valent halides CsTi 2 I 7 (tetrahedra and octahedra) and Na 5 Ti 3 Cl 12 (chains of octahedra) have been observed. Except for the triangles in titanium(II) halides, cluster compounds are rare but include K 4 [{OTi 4 }I 12 ] and {CTi 6 }Cl 14 .