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Titanium Triamidotriamine Compounds: Syntheses, Structures and Redox Properties
Author(s) -
Martins Ana M.,
Ascenso José R.,
de Azevedo Cristina G.,
Dias Alberto R.,
Duarte M. Teresa,
Ferreira Humberto,
Ferreira M. João,
Henriques Rui T.,
Lemos M. Amélia,
Li Li,
da Silva João F.
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400813
Subject(s) - chemistry , titanium , redox , metal , enantiomer , medicinal chemistry , trigonal crystal system , crystallography , nitrogen , sodium , stereochemistry , crystal structure , inorganic chemistry , organic chemistry
The preparation of 1,4,7‐{NH(2‐C 6 H 4 F)SiMe 2 } 3 ‐1,4,7‐triazacyclononane (H 3 N 3‐F [9]N 3 ) and 1,4,8‐{N(H)PhSiMe 2 } 3 ‐1,4,8‐triazacycloundecane (H 3 N 3 [11]N 3 ), and their sodium derivatives Na 3 N 3‐F [9]N 3 (THF) 2 and Na 3 N 3 [11]N 3 (THF) 2 , is described. The reaction of [TiCl 3 (THF) 3 ] with Na 3 N 3‐F [9]‐N 3 (THF) 2 and Na 3 N 3 [11]N 3 (THF) 2 leads to [Ti{N 3‐F [9]N 3 }] and [Ti{N 3 [11]N 3 }]. The titanium complexes react readily with I 2 to give the Ti IV derivatives [Ti{N 3‐F [9]N 3 }]I and [Ti{N 3 [11]N 3 }]I. All titanium compounds display distorted trigonal prismatic geometries where the metal is coordinated to the six nitrogen donors. Fluxional processes that convert the conformations of the five‐ and six‐membered metallacycles and the Δ and Λ enantiomers of [Ti{N 3 [11]N 3 }]I have been identified in solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)