P. Jeske et al., SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR OCTAHEDRAL TITANIUM(IV)COMPLEXES CONTAINING TI=O, TI(O2), AND TI(OCH3)X (X=1-3) STRUCTURAL UNITS, Inorganic chemistry, 33(11), 1994, pp. 2462-2471
The oxidation of [(Me3tacn)TiIIIBr3] (where Me3tacn is 1,4,7-trimethyl
-1,4,7-triazacyclononane) in water with Na2[S2O8] yields upon addition
of NaClO4 yellow-orange [(Me3tacn)TiIVBr3]ClO4 (1). The series [(Me3t
acn)TiIVBrx(OCH3)(3-x)]+ (x = 2 (2); x = 1 (3); x = 0 (4)) has been sy
nthesized by oxidation reactions of [(Me3tacn)TiBr3] with air in aceto
nitrile/methanol mixtures and methanol as solvents. Complexes 1, [(Me3
tacn)-TiBr(OCH3)2](ClO4) (3), and [(Me3tacn)Ti(OCH3)3]BPh4 (4) have be
en structurally characterized by X-ray crystallography. Crystal data:
for 1, monoclinic P2(1)/n, a = 11.146(6) angstrom, b = 12.640(5) angst
rom, c = 12.871(5) angstrom, beta = 91.19(4)degrees, V = 1812.9 (14) a
ngstrom3, Z = 4; for 3, monoclinic P2(1)/c; a = 11.837 (3) angstrom, b
= 12.63 5 (3) angstrom, c = 13.044(2) angstrom, beta = 92.34(2)degree
s, V = 1949.2(9) angstrom3, Z = 4; for 4, monoclinic P2(1)/n, a = 10.3
94(2) angstrom, b = 21.483(4) angstrom, c = 15.741(3) angstrom, beta =
90.30(3)degrees, V = 3514.8(12) angstrom3, Z = 4. Two orange-red pero
xotitanium(IV) complexes [(Me3tacn)Ti(O2)(NCO)2] (5) and [(Me3tacn)Ti(
O2)Cl2] (6) have been isolated from acetonitrile solutions of [(Me3tac
n) 2Ti2III(NCO)4(mu-O)] and [(Me3tacn)TiCl3] Which had been exposed to
air and H2O2, respectively. Crystal data for 5: monoclinic P2(1)/n, a
= 8.602(3) angstrom, b = 12.478(5), c = 14.671(4) angstrom, beta = 91
.18(3)degrees, V = 1574.4(12) angstrom3, Z = 4. Complexes 5 and 6 cont
ain an eta2-O2(2-) ligand. Three new octahedral titanyl complexes, [(M
e3tacn)-Ti(O)Cl2] (7), [(tiptacn)Ti(O)(NCS)2] (8), and [(tiptacn)Ti(O)
(NCO)2] (9), were obtained from acetonitrile solutions of [(Me3tacn)Ti
Cl3], [(tiptacn)Ti(NCS)3], and [(tiptacn)Ti(NCO)2(OCH3)] by interactio
n with oxygen where tiptacn represents 1,4,7-isopropyl-1,4,7-triazacyc
lononane. Crystal data for 7: monoclinic P2(1)/a, a = 12.815-(3) angst
rom, b = 7.829(2) angstrom, c = 15,146(6) angstrom, beta = 114.67(3)de
grees, V = 1380.9(10) angstrom3, Z = 4. The Ti=O distance was found to
be 1.637(3) angstrom. All new compounds have been studied by infrared
and Raman spectroscopy in solution and in the solid state.