Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring s-Hydrindacene Skeleton

Abstract

The bulky aryl alcohols, (Rind)OH (1) [Rind = EMind (a) and Eind (b)], based on the rigid fused-ring 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacene skeleton were prepared by the reaction of (Rind)Li with nitrobenzene followed by protonation. The treatment of 1 with (n)BuLi affords the lithium aryloxide dimers [(Rind)OLi(THF)]2 (2) or trimers [(Rind)OLi]3 (3), depending on the employed solvents (THF = tetrahydrofuran). The salt metathesis reaction of [(EMind)OLi(THF)]2 (2a) with TiCl4(THF)2 leads to the formation of the mononuclear diamagnetic mono- and bis(aryloxide) Ti(IV) complexes, [(EMind)O]TiCl3(THF) (4a) and [(EMind)O]2TiCl2 (5a). We also isolated a trace amount of the tris(aryloxide) Ti(IV) complex, [(EMind)O]3TiCl (6a). The reaction between 2a and TiCl3(THF)3 resulted in the isolation of the mononuclear paramagnetic mono- and bis(aryloxide) Ti(III) complexes, [(EMind)O]TiCl2(THF)2 (7a) and [(EMind)O]2TiCl(THF)2 (8a). The discrete monomeric structures of the titanium complexes 4a, 5a, 6a, 7a, and 8a were determined by X-ray crystallography.

Low‐Coordinated Titanium(III) Alkyl—Molecular and Surface—Complexes: Detailed Structure from Advanced EPR Spectroscopy

“…[9] Most of them involve cyclopentadienyl ligands, [10] though there are few exceptions. [11] Nevertheless,there are no reports of titanium(III) alkyl species using alkoxide ligands,t hat would constitute reasonable models for surface titanium(III) alkyl species.Wereason that sterically shielding ligands would avoid the formation of ate or multinuclear complexes and that tris-tert-butoxysiloxy ligands,m imicking the silica surface, [12] or larger aryloxy ligands [13] could afford good models of the surface titanium(III) alkyl sites.…”

Recycling primary lithium batteries using a coordination chemistry approach: recovery of lithium and manganese residues in the form of industrially important materials

“…39–45 Dinuclear lithium aryloxides are usually formed using bulk phenolato ligands, i.e. , [Li 2 (OAr) 2 X 2 ] where ArO − = 2,6-di- t -butyl-4-methylphenolato, 46,47 2,6-di- t -butylphenolato, 48,49 2,6-dibenzylphenolato, 50 2,6-di- t -butylphenolato, 51 3,6-di- t -butyl-1-(isoquinolin-1-yl)-2-naphtholato- N , O , O , 52 and 1,1,7,7-tetraethyl-3,3,5,5-tetramethyl-1,2,3,5,6,7-hexahydro- s -indacen-4-olato, 53 and X = Et 2 O, THF, DME, and DMSO; or Mannich, 54–56 and Schiff base ligands. 57–59 Only three lithium phenolate dimers [Li 2 (OAr) 2 (H 2 O) x ] (where ArO − = 2-bromophenolato and x = 4; 2,4,6-trinitrophenolato and x = 2), 60,61 and [Li 2 (OAr) 2 (H 2 O) 2 ] n (where ArO − = 1-oxo-1 H -phenalen-9-olato), 62 containing Li coordinated with H 2 O in a similar manner to that in 4 have been reported.…”

“…Monomeric lithium aryloxides are obtained when steric monoor poly-phenolato ligands are used in the presence of strong donor solvents (ethers, amines, alcohols). [39][40][41][42][43][44][45] Dinuclear lithium aryloxides are usually formed using bulk phenolato ligands, i.e., [Li 2 (OAr) 2 X 2 ] where ArO − = 2,6-di-t-butyl-4-methylphenolato, 46,47 2,6-di-t-butylphenolato, 48,49 2,6-dibenzylphenolato, 50 2,6-di-t-butylphenolato, 51 3,6-di-t-butyl-1-(isoquinolin-1yl)-2-naphtholato-N,O,O, 52 and 1,1,7,7-tetraethyl-3,3,5,5-tetramethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-olato, 53 and X = Et 2 O, THF, DME, and DMSO; or Mannich, [54][55][56] and Schiff base ligands. [57][58][59] Only three lithium phenolate dimers [Li 2 (OAr) 2 (H 2 O) x ] (where ArO − = 2-bromophenolato and x = 4; Scheme 1 The general route for the synthesis of metal aryloxides from lithium batteries.…”

Crystal structure of a rare trigonal bipyramidal titanium(IV) coordination complex: trichlorido(3,3′-di-tert-butyl-2′-hydroxy-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2-olato-κO2)(tetrahydrofuran-κO)titanium(IV)

“…The structure of BIPHEN(TiCl 3 ) 2 comprises TiCl 3 moieties additionally coordinated by each phenoxide O atom of the ligand (Chisholm et al, 2003). A very similar structure to the title compound, [(EMind)O]-TiCl 3 (THF), also has a bulky phenoxide ligand in an equatorial position and THF in an axial position on the trigonalbipyramid (Kanazawa et al, 2016). Also similar, the same trigonal-bipyramidal arrangement is seen in a complex with two TiCl 3 (ethyl acetate) units coordinated by phenoxides derived from the diol 2,2 0 -(1,3-butadiyne-1,4-diyl)bis[phenol] (Saied et al, 1998a).…”