Synthesis of arene Ti and Zr complexes and their reactivity towards air: crystal structure of [(C6H3Me3)2Zr(AlCl4)](A12Cl7) and TiCl3(OPh)

Synthesis and spectroscopic characterization of aryloxide derivatives of titanium(IV) and zirconium(IV)

“…Derivatives (1), (2), (5)À(9), (11), (13), (14), and (17) are dimeric (ebullioscopically), whereas (3), (4), (12), (15), (16), (18), and (19) are monomeric in benzene solution.…”

“…The structures of titanium and zirconium aryloxides often depend on the nature of aryloxide ligands and their stoichiometry [1], as is depicted by following typical examples:[Ti(l-Cl) 2 Cl(OPh)] µ [15], [TiCl 2 (OPh)-(l-OPh)] 2 [16], [Ti(OPh) 3 (l-OPh)(PhOH)] 2 [17], [Ti (OAr) 4 ] (OAr ¼ C 6 H 3 Pr i 2 -2,6; C 6 H 4 Bu t -2, C 6 HMe 4 -2,3,5,6) [18,19], and [ZrCl 2 (OC 6 H 3 Me 2 -2,6) 2 (thf)] [20].…”

“…(3), (4),(12),(15),(16),(18), and(19) can be formulated as monomers: [Ti(OPr i )(OAr 5 ) 3 ](3), [Ti(OAr 5 ) 4 ](4), [TiCl 2 (OAr 4 ) 2 ](12), [TiCl(OAr 5 ) 3 ](15), [ZrCl(OAr 5 ) 3 (thf)](16), [TiCl 3 (OAr 1 )(thf) 2 ](18), and [TiCl 2 (OAr 4 ) 2 (thf) 2 ](19), whereas other derivatives appear to adopt dimeric structures: [Ti(OPr i ) 2 (lOPr i )(OAr 5 )] 2 (1), [Ti(OPr i )(l-OPr i )(OAr 5 ) 2 ] 2 (2), [Ti(l-…”