Sc. Dunn et al., CYCLOPENTADIENYL, INDENYL AND BIS(CYCLOPENTADIENYL) TITANIUM IMIDO COMPOUNDS, Journal of the Chemical Society. Dalton transactions, (3), 1997, pp. 293-304
The titanium tert-butyl imido compounds [Ti(NBu(t))Cl-2(NC(5)H(4)R-4)(
n)] (R = H, n = 2 or 3; R = Bu(t), n = 2) have been found to be entry
points to the half-sandwich eta(5)-cyclopentadienyl derivatives [Ti(et
a(5)-C(5)R'(4)R '')(NBu(t))Cl(NC(5)H(4)R-4)] (R = Bu(t), R' = R '' = H
or Me; R = H, R' = H, R '' = H, Me or Pr-i; R = H, R' = Me, R '' = Me
, Et or C4H7), the eta(5)-1,2,3 -trimethylindenyl species [Ti(eta(5)-C
(9)H(4)Me(3)) (NBu(t))Cl(NC(5)H(4)Bu(t)-4)] and the bis(eta(5) 5-cyclo
pentadienyl) compound [Ti(eta(5)-C5H5)(2)(NBu(t)(NC5H5)], the crystal
structure of which has been determined. The complex [Ti(eta(5)-C5H5)(N
Bu(t))Cl(NC5H5)] readily loses pyridine under vacuum in the solid Stat
e to form the binuclear complex [Ti-2(eta(5)-C5H5)(2)(mu-NBu(t))(2)Cl-
2]. Treatment of [Ti(eta(5)-C(5)Me(4)R)(NBu(t))Cl(NC5H5)] (R = Me or E
t) with Na[C5H5] gives the corresponding mixed-ring sandwich derivativ
es eta(5)-C5H5)(eta(5)-C(5)Me(4)R)(NBu(t))Cl(NC5H5)]. Addition of Li[C
9H7] to [Ti(eta(5)-C5H5)(NBu(t))Cl(NC5H5)] gave the eta(5)-cyclopentad
ienyl, eta(3)-indenyl mixed-ring analogue [Ti(eta(5)-C5H5)(eta(3)-C9H7
)(NBu(t))(NC5H5)]. The complex [Ti(eta(5)-C5H5)(2)(NBu(t))(NC5H)] unde
rgoes a room-temperature cyclopentadienyl ligand-redistribution reacti
on with [Ti(NBu(t))Cl-2(NC5H5)(2)] forming [Ti(eta(5)-C5H5)(NBu(t))Cl(
NC5H5)] in quantitative yield. Variable-temperature NMR spectra for th
e half-sandwich complexes show that the co-ordinated pyridine exchange
s with free pyridine via an associative mechanism. The compound i(eta(
5)-C5H5)(eta(5)-C(5)Me(4)Et)(NBu(t))(NC5H5)] is also fluxionaI and exh
ibits reversible pyridine dissociation at higher temperatures and rest
ricted rotationabout the Ti-N (pyridine) bond at lower temperatures.