74481-90-6Relevant academic research and scientific papers
TRANSITION-METAL COMPLEXES OF TWO VALENCE TAUTOMERS OF A BULKY PHENOXIDE, 2,6--Bu-t2-4-MeC6H2O- (ArO-); PREPARATION AND CRYSTAL AND MOLECULAR STRUCTURE OF A PHENOXYTITANIUM(III) AND A CYCLOHEXADIENONYLRHODIUM(I) COMPLEX, AND 5)(PPh3)2>
Cetinkaya, B.,Hitchcock, P. B.,Lappert, M. F.,Torroni, S.,Atwood, J. L.,et. al.
, p. C31 - C35 (1980)
The 2,6-di-t-butyl-4-methylphenoxo ligand (ArO-) is ambidentate, giving rise to the O-bonded 15-electron d1 and the η5--bonded 18-electron d8 complex 5)(PPh3)2>, obtained from 2>-LiOAr and (PPh3)2>-ArOH, respectively; the average Ti-C(η) distance is 2.362(10) Angstroem, Ti-O 1.892(2) Angstroem, and O-C(of Ar) 1.352(3) Angstroem, and TiOC 142.3(2) deg; in the RhI complex, C(2)-C(6) are coplanar (with C-C(av.) 1.38(2) Angstroem), C(1)-O 1.28 Angstroem, and Rh to C(2)-C(6) bond lengths are in the range 2.19-2.65 Angstroem.
Bulky Metal Aryloxides, Arylamides, and Sulphur and Phosphorus Analogues Part 1. Synthetic and Chemical Studies of Titanium and Zirconium Aryloxides
Duff, Alan W.,Kamarudin, Rose A.,Lappert, Michael F.,Norton, Reginald J.
, p. 489 - 498 (2007/10/02)
The synthesis and characterisation of several classes of aryloxides (OR) of TiIV, TiIII, ZrIV, and Li are described.Those of TiIV are of eight distinct classes: , , , , , , , and (R' = alkyl, thf = tetrahydrofuran); the TiIII complexes are of types n> and ; the ZrIV complexes are of seven types: and , with X = OR, Cl, NMe2, OMe, OC(O)NMe2, or N(Ph)CNMe2; the new lithium aryloxides have formula n.Most of the results relate to the ligands 2,6-Me2C6H3O-, 2,6-Pri2C6H3O-, 2,6-But2C6H3O-, 4-Me-2,6-But2C6H2O-, 2,4,6-But3C6H2O-, 3,5-ButC6H3O-, and 2,4-But2C6H3O-.The new complexes are readily soluble in diethyl ether and many also in hydrocarbons.Synthetic procedures include the following systems: (i) LiBun-ROH-OEt2, for Li aryloxides; (ii) TiIV, TiIII, or ZrIV chlorides with n; (iii) for TiIII, a redox reaction of type (ii) using a TiIV chloride as precursor; (iv) a TiIV or ZrIV dimethylamide and ROH; and (v) for the ZrIV carbamate or ZrIV urea, a CO2 or PhNCO insertion into the appropriate ZrIV dimethylamide.
