Synthesis, characterization, volatilization, alcoholysis and hydrolytic studies of nonaalkoxodititanatocopper(II) complexes

Abstract

Heterobimetallic alkoxides of Cu(II) of the types [Cu{g 4 -Ti 2 (OEt) 9 }Cl] (1) and [Cu{g 3 -Ti 2 (OR) 9 } 2 ] [R = Pr i (2), R = Et(3)] have been prepared for the first time by the reactions of CuCl 2 AE xROH with KTi 2 (OR) 9 in 1:1 and 1:2 molar ratios, respectively, in benzene medium. The chloro(nonaalkoxo dititanato)copper (II) complexes undergo chloride replacement reactions by a variety of monodentate alkoxo ( ) OPr i , ) OEt) and chelating [Al(OPr i ) 4 ) , Al(OEt) 4 ) , Nb(OPr i ) 6 ) , Zr 2 (OPr i ) 9 ) , Sn 2 (OPr i ) 9 ), and Sn 2 (OEt) 9 ) ] ligands to form interesting hetero(bi-and tri-)metallic complexes. Alcoholysis (with methyl alcohol and tert-butyl alcohol) and hydrolytic [with Ba(OH) 2 AE 8H 2 O powder] reactions of a few typical compounds have also been investigated. All of these have been characterized by elemental analyses, molecular weight determinations, spectral (i.r. and visible) and magnetic studies. On attempted volatilization under reduced pressure these complexes liberated titanium alkoxides as a volatile component leaving nonvolatile residues.

Single-Source Materials for Metal-Doped Titanium Oxide: Syntheses, Structures, and Properties of a Series of Heterometallic Transition-Metal Titanium Oxo Cages

“…It has been reported previously that the 1:1 or 2:1 stoichiometric reactions of [KTi 2 (OR) 9 ] ( A ) in benzene with a series of divalent metal salts [MCl 2 ] give complexes in which the dinuclear [Ti 2 (OR) 9 ] − anion is transferred intact to the metal ions. , In particular, the trinuclear Co II complex [Ti 2 (OEt) 9 (CoCl)], whose structure is assumed to be related to the structurally characterized complex [Ti 2 (O i Pr) 9 (CuCl)], was prepared via the reaction of [KTi 2 (OEt) 9 ] with CoCl 2 (Scheme a)…”

Extending the Family of Titanium Heterometallic–oxo–alkoxy Cages

“…The larger octanuclear cage [Ti 7 CoO 5 (O Et ) 19 Cl] ( 1 ) was also obtained (unexpectedly) in low yield from the reaction of [K{Ti 2 (O Et ) 9 }] with [CoCl 2 ] in toluene, but the mechanism involved in its formation was unclear . Other heterometallic cages containing Ti or Zr have also been reported, such as [Co 2 Ti 2 ( acac ) 2 (O i Pr ) 10 ], [Pb 2 Ti 2 O(O i Pr ) 10 ], [Tm{Ti 2 (O R ) 9 }Xl] x [Tm = Cu, Co, Ni, Sn, Pb; Xl = halogen], − [Ti 4 ( N , N -dimethylaminoethanolate)(OH)O 6 Cu 6 (benzoate) 9 ], and [Sr 2 Zr 2 (OH) 2 (O i Pr ) 10 ( i Pr OH) 4 ] …”

Heterometallic cobalt(ii)–titanium(iv) oxo cages; key building blocks for hybrid materials

“…We report here our first steps in this aim, with the synthesis and characterisation of the first Co II It has been reported that the 1 : 1 or 2 : 1 stoichiometric reactions of [KTi 2 (OR) 9 ] with a series of divalent metal salts give complexes in which the dinuclear [Ti 2 (OR) 9 ] À anion is transferred intact to the metal ions. 15,16 Most pertinent to our current study, the trinuclear Co II complex [Ti 2 (OEt) 9 (CoCl)], whose structure is assumed to be related to the structurally characterised complex [Ti 2 (O i Pr) 9 (CuCl)], 17 was prepared via the reaction of [KTi 2 (OEt) 9 ] with CoCl 2 (Scheme 1a). 15 In initial work in this area we decided to prepare this complex as a precursor to hybrid materials.…”