TY - JOUR
T1 - Synthesis, characterization, and reactions of monomeric titanium complexes containing a chelating bis(phenolate) ligand [1, 2]
AU - Toscanck, Paul J.
AU - Schermerhorn, E. James
AU - Barren, Elizabeth
AU - Liu, Shuncheng
AU - Zubieta, Jon
PY - 1998
Y1 - 1998
N2 - The synthesis of Ti(iso)Cl2 (iso = the dianion of 2,2′-ethylidenebis(4,6-di-tert-butylphenol)) is described. Metathesis reactions of this complex with Grignard reagents, as well as alkali metal salts, yielded Ti(iso)X2 (X = CH3, CH2Ph, CH2SiMe3, OCMe3, or NMe2). Reactions of the Ti-C bond in Ti(iso)(CH3)2 toward halogens, active hydrogen compounds, and acetone were studied. In addition, Ti(iso)(X)(Y) (X = Cl or CH3; Y = OC6H2-2 , 6-tBu2-4-Me) could be prepared with the formation of only one coordination isomer. The new complexes have been thoroughly characterized by 1H and 13C NMR spectroscopies. The solid state structure of Ti(iso)Cl2 was determined via single crystal X-ray diffraction methods. The complex is monomeric, with approximately tetrahedral geometry about the titanium ion. The structure of Ti(iso)Cl2 is compared to that of Ti(ultra)Cl2 (ultra = the dianion of 2,2′-methylenebis(6-tert-buty]-4-methylphenol)), which was redetermined to greater precision.
AB - The synthesis of Ti(iso)Cl2 (iso = the dianion of 2,2′-ethylidenebis(4,6-di-tert-butylphenol)) is described. Metathesis reactions of this complex with Grignard reagents, as well as alkali metal salts, yielded Ti(iso)X2 (X = CH3, CH2Ph, CH2SiMe3, OCMe3, or NMe2). Reactions of the Ti-C bond in Ti(iso)(CH3)2 toward halogens, active hydrogen compounds, and acetone were studied. In addition, Ti(iso)(X)(Y) (X = Cl or CH3; Y = OC6H2-2 , 6-tBu2-4-Me) could be prepared with the formation of only one coordination isomer. The new complexes have been thoroughly characterized by 1H and 13C NMR spectroscopies. The solid state structure of Ti(iso)Cl2 was determined via single crystal X-ray diffraction methods. The complex is monomeric, with approximately tetrahedral geometry about the titanium ion. The structure of Ti(iso)Cl2 is compared to that of Ti(ultra)Cl2 (ultra = the dianion of 2,2′-methylenebis(6-tert-buty]-4-methylphenol)), which was redetermined to greater precision.
KW - Bidentate diphenolate ligands
KW - Eight-membered rings
KW - Titanium complexes
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U2 - 10.1080/00958979808022665
DO - 10.1080/00958979808022665
M3 - Article
AN - SCOPUS:2542582395
SN - 0095-8972
VL - 43
SP - 169
EP - 185
JO - Journal of Coordination Chemistry
JF - Journal of Coordination Chemistry
IS - 2-3
ER -