metal-organic compounds
Bis(μ2-isopropylimido-κ2N:N)bis[(η5-cyclopentadienyl)(ethenolato-κO)titanium(IV)]
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
*Correspondence e-mail: martin.haehnel@catalysis.de
The title dinuclear half-sandwich complex, [CpTi(OCH=CH2)(μ2-N-iPr)]2 (Cp = cyclopentadienyl; iPr = isopropyl), was obtained from the reaction of Cp2TiCl2, n-butyllithium and isopropylamine in tetrahydrofuran. Each TiIV atom is coordinated by one Cp ligand, one vinyloxy unit and two bridging imido groups in a strongly distorted tetrahedral geometry. There are two half molecules in the such that whole molecules being generated by inversion symmetry.
CCDC reference: 975548
Related literature
For other Ti complexes with both Cp′ (Cp′ = substituted or unsubstituted Cp) ligands and an enolate unit with a terminal =CH2 group, see: Curtis et al. (1984); Veya et al. (1993); Beckhaus et al. (1994); Schwartz et al. (1996). For selected examples of half-sandwich CpTi complexes with μ2-bridging imido ligands, see: Vroegop et al. (1983); Grigsby et al. (1996); Ascenso et al. (2001); Tsurugi et al. (2011).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2005); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 975548
https://doi.org/10.1107/S1600536813033072/pk2508sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033072/pk2508Isup2.hkl
To a stirred solution of isopropylamine (0.3 ml, 3.5 mmol) in 20 ml of THF was added a solution of n-butyllithium (1.6 M, 5.0 ml) in n-hexane at room temperature. After stirring fo 16 h, the reaction mixture was slowly poured into a suspension of Cp2TiCl2 (872 mg, 3.5 mmol) in 15 ml of THF. Immediately, the colour turned dark brown. After additional stirring for 20 h, all volatiles were removed in vacuum and the dark brown residue was suspended in 40 ml of diethylether and filtered. The dark brown solution was then concentrated to 5 ml and stored at -78 °C for 3 days to give dark red crystals of the title compound, suitable for X-ray analysis, which were filtered, washed with cold toluene and dried in vacuum (yield: 256 mg, 34%)
H atoms were placed in idealized positions with d(C—H) = 0.95 - 1.00 Å (CH), 0.95 Å (CH2) and 0.98 Å (CH3) and refined using a riding model with Uiso(H) fixed at 1.2 Ueq(C) for CH, CH2 and 1.5 Ueq(C) for CH3.
The reaction of Cp2TiCl2, n-butyllithium and isopropylamine in THF was investigated to synthesize the new titanocene imido compound Cp2Ti=N-iPr. However, the excess of n-butyllithium led to THF cleavage, involving the formation of vinyloxy species. Substitution of one of the Cp ligands by the vinyloxy ligand was observed, together with the imido unit bridging over two titanium centers, thus forming a dinuclear complex. The
contains two half molecules of the title compound. Each titanium center is coordinated by one Cp ligand, one vinyloxy unit and two bridging imido groups (Fig. 1). The geometry at the titanium centers is strongly distorted tetrahedral. The largest deviation from the ideal tetrahedral angle is observed for N2—Ti2—N2A with 85.84 (4)°. The central four-membered metallacycles Ti1, N1, Ti1A, N1A and Ti2, N2, Ti2A, N2A are planar by virtue of the inversion symmetry.For other Ti complexes with both Cp' (Cp' = substituted or unsubstituted Cp) ligands and an enolate unit with a terminal ═CH2 group, see: Curtis et al. (1984); Veya et al. (1993); Beckhaus et al. (1994); Schwartz et al. (1996). For selected examples of half-sandwich CpTi complexes with µ2-bridging imido ligands, see: Vroegop et al. (1983); Grigsby et al. (1996); Ascenso et al. (2001); Tsurugi et al. (2011).
Data collection: X-AREA (Stoe & Cie, 2005); cell
X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Ti2(C5H5)2(C3H7N)2(C2H3O)2] | F(000) = 896 |
Mr = 426.26 | Dx = 1.338 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8746 (4) Å | Cell parameters from 4113 reflections |
b = 9.7484 (2) Å | θ = 2.5–29.5° |
c = 16.3264 (4) Å | µ = 0.77 mm−1 |
β = 106.593 (2)° | T = 150 K |
V = 2116.27 (9) Å3 | Prism, brown |
Z = 4 | 0.50 × 0.40 × 0.25 mm |
Stoe IPDS II diffractometer | 4211 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 27.0°, θmin = 1.7° |
ω scans | h = −17→17 |
32869 measured reflections | k = −12→12 |
4625 independent reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0485P)2 + 0.2691P] where P = (Fo2 + 2Fc2)/3 |
4625 reflections | (Δ/σ)max = 0.002 |
239 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
[Ti2(C5H5)2(C3H7N)2(C2H3O)2] | V = 2116.27 (9) Å3 |
Mr = 426.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.8746 (4) Å | µ = 0.77 mm−1 |
b = 9.7484 (2) Å | T = 150 K |
c = 16.3264 (4) Å | 0.50 × 0.40 × 0.25 mm |
β = 106.593 (2)° |
Stoe IPDS II diffractometer | 4211 reflections with I > 2σ(I) |
32869 measured reflections | Rint = 0.031 |
4625 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.41 e Å−3 |
4625 reflections | Δρmin = −0.37 e Å−3 |
239 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.00508 (9) | 0.81266 (12) | 0.07526 (8) | 0.0264 (2) | |
H1 | 1.0139 | 0.8211 | 0.0199 | 0.032* | |
C2 | 1.04722 (11) | 0.90582 (14) | 0.13237 (9) | 0.0398 (3) | |
H2A | 1.0400 | 0.9008 | 0.1884 | 0.048* | |
H2B | 1.0849 | 0.9783 | 0.1176 | 0.048* | |
C3 | 1.10447 (9) | 0.42926 (12) | 0.16322 (7) | 0.0237 (2) | |
H3 | 1.0485 | 0.4372 | 0.1903 | 0.028* | |
C4 | 1.14785 (12) | 0.28630 (14) | 0.18057 (9) | 0.0406 (3) | |
H4A | 1.0950 | 0.2187 | 0.1567 | 0.061* | |
H4B | 1.1743 | 0.2723 | 0.2424 | 0.061* | |
H4C | 1.2023 | 0.2753 | 0.1539 | 0.061* | |
C5 | 1.18229 (11) | 0.53813 (14) | 0.20265 (8) | 0.0344 (3) | |
H5A | 1.2402 | 0.5285 | 0.1801 | 0.052* | |
H5B | 1.2043 | 0.5268 | 0.2649 | 0.052* | |
H5C | 1.1526 | 0.6294 | 0.1884 | 0.052* | |
C6 | 0.83879 (9) | 0.43737 (12) | 0.13292 (7) | 0.0252 (2) | |
H6 | 0.8677 | 0.4425 | 0.1931 | 0.030* | |
C7 | 0.77320 (9) | 0.53364 (12) | 0.08185 (8) | 0.0273 (2) | |
H7 | 0.7498 | 0.6153 | 0.1015 | 0.033* | |
C8 | 0.74794 (9) | 0.48839 (13) | −0.00364 (8) | 0.0273 (2) | |
H8 | 0.7049 | 0.5344 | −0.0516 | 0.033* | |
C9 | 0.79764 (8) | 0.36312 (12) | −0.00555 (7) | 0.0249 (2) | |
H9 | 0.7938 | 0.3094 | −0.0549 | 0.030* | |
C10 | 0.85404 (8) | 0.33132 (12) | 0.07872 (7) | 0.0241 (2) | |
H10 | 0.8951 | 0.2525 | 0.0961 | 0.029* | |
C11 | 0.49256 (11) | −0.21964 (14) | 0.14913 (8) | 0.0350 (3) | |
H11 | 0.4293 | −0.2371 | 0.1088 | 0.042* | |
C12 | 0.54472 (15) | −0.32585 (17) | 0.18746 (11) | 0.0544 (4) | |
H12A | 0.6083 | −0.3125 | 0.2281 | 0.065* | |
H12B | 0.5188 | −0.4160 | 0.1745 | 0.065* | |
C13 | 0.69659 (8) | −0.08443 (12) | 0.03329 (7) | 0.0232 (2) | |
H13 | 0.6907 | −0.1851 | 0.0212 | 0.028* | |
C14 | 0.75543 (10) | −0.02130 (15) | −0.02278 (9) | 0.0331 (3) | |
H14A | 0.7197 | −0.0378 | −0.0830 | 0.050* | |
H14B | 0.8224 | −0.0631 | −0.0093 | 0.050* | |
H14C | 0.7622 | 0.0777 | −0.0122 | 0.050* | |
C15 | 0.75381 (10) | −0.06547 (16) | 0.12745 (8) | 0.0356 (3) | |
H15A | 0.7647 | 0.0326 | 0.1400 | 0.053* | |
H15B | 0.8189 | −0.1123 | 0.1397 | 0.053* | |
H15C | 0.7146 | −0.1045 | 0.1631 | 0.053* | |
C16 | 0.59925 (10) | 0.27006 (13) | 0.09822 (8) | 0.0324 (3) | |
H16 | 0.6481 | 0.2876 | 0.0689 | 0.039* | |
C17 | 0.61833 (10) | 0.21581 (14) | 0.18150 (8) | 0.0344 (3) | |
H17 | 0.6823 | 0.1899 | 0.2179 | 0.041* | |
C18 | 0.52699 (10) | 0.20677 (13) | 0.20118 (7) | 0.0311 (3) | |
H18 | 0.5181 | 0.1745 | 0.2535 | 0.037* | |
C19 | 0.45087 (9) | 0.25346 (12) | 0.13058 (8) | 0.0278 (2) | |
H19 | 0.3812 | 0.2576 | 0.1264 | 0.033* | |
C20 | 0.49548 (10) | 0.29353 (12) | 0.06639 (8) | 0.0290 (2) | |
H20 | 0.4614 | 0.3297 | 0.0118 | 0.035* | |
N1 | 1.06135 (7) | 0.44839 (9) | 0.07062 (6) | 0.02088 (18) | |
N2 | 0.59469 (7) | −0.02696 (9) | 0.01025 (6) | 0.02089 (19) | |
O1 | 0.95030 (6) | 0.70628 (8) | 0.08943 (5) | 0.02590 (17) | |
O2 | 0.52192 (6) | −0.08863 (9) | 0.16262 (5) | 0.02749 (18) | |
Ti1 | 0.924511 (14) | 0.532856 (19) | 0.036855 (12) | 0.01873 (7) | |
Ti2 | 0.520839 (14) | 0.05278 (2) | 0.083057 (12) | 0.01907 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0297 (6) | 0.0218 (5) | 0.0307 (6) | −0.0005 (4) | 0.0136 (5) | 0.0008 (4) |
C2 | 0.0497 (8) | 0.0313 (7) | 0.0409 (7) | −0.0158 (6) | 0.0170 (6) | −0.0048 (5) |
C3 | 0.0243 (5) | 0.0265 (5) | 0.0189 (5) | 0.0013 (4) | 0.0038 (4) | 0.0020 (4) |
C4 | 0.0452 (8) | 0.0312 (7) | 0.0392 (7) | 0.0105 (6) | 0.0020 (6) | 0.0085 (5) |
C5 | 0.0363 (7) | 0.0388 (7) | 0.0224 (6) | −0.0076 (5) | −0.0010 (5) | −0.0016 (5) |
C6 | 0.0251 (5) | 0.0286 (6) | 0.0236 (5) | −0.0064 (4) | 0.0095 (4) | 0.0016 (4) |
C7 | 0.0257 (6) | 0.0252 (6) | 0.0347 (6) | −0.0023 (4) | 0.0143 (5) | 0.0006 (4) |
C8 | 0.0207 (5) | 0.0302 (6) | 0.0295 (6) | −0.0024 (4) | 0.0049 (4) | 0.0067 (5) |
C9 | 0.0241 (5) | 0.0252 (5) | 0.0255 (5) | −0.0081 (4) | 0.0073 (4) | −0.0012 (4) |
C10 | 0.0229 (5) | 0.0214 (5) | 0.0287 (5) | −0.0040 (4) | 0.0085 (4) | 0.0035 (4) |
C11 | 0.0456 (7) | 0.0327 (7) | 0.0274 (6) | −0.0083 (5) | 0.0115 (5) | 0.0013 (5) |
C12 | 0.0804 (12) | 0.0327 (8) | 0.0472 (9) | 0.0012 (8) | 0.0135 (8) | 0.0030 (6) |
C13 | 0.0202 (5) | 0.0248 (5) | 0.0243 (5) | 0.0029 (4) | 0.0056 (4) | 0.0009 (4) |
C14 | 0.0251 (6) | 0.0422 (7) | 0.0344 (7) | 0.0009 (5) | 0.0125 (5) | 0.0040 (5) |
C15 | 0.0239 (6) | 0.0536 (8) | 0.0260 (6) | 0.0080 (5) | 0.0018 (5) | 0.0013 (5) |
C16 | 0.0336 (6) | 0.0290 (6) | 0.0376 (7) | −0.0114 (5) | 0.0151 (5) | −0.0100 (5) |
C17 | 0.0317 (6) | 0.0356 (7) | 0.0307 (6) | −0.0024 (5) | 0.0006 (5) | −0.0136 (5) |
C18 | 0.0449 (7) | 0.0275 (6) | 0.0219 (5) | 0.0021 (5) | 0.0112 (5) | −0.0057 (4) |
C19 | 0.0324 (6) | 0.0229 (5) | 0.0304 (6) | 0.0021 (4) | 0.0128 (5) | −0.0038 (4) |
C20 | 0.0398 (7) | 0.0203 (5) | 0.0272 (6) | −0.0017 (5) | 0.0102 (5) | −0.0002 (4) |
N1 | 0.0226 (4) | 0.0200 (4) | 0.0188 (4) | −0.0035 (3) | 0.0040 (4) | 0.0004 (3) |
N2 | 0.0197 (4) | 0.0225 (5) | 0.0204 (4) | 0.0011 (3) | 0.0057 (4) | 0.0004 (3) |
O1 | 0.0328 (4) | 0.0215 (4) | 0.0257 (4) | −0.0057 (3) | 0.0119 (3) | −0.0039 (3) |
O2 | 0.0341 (4) | 0.0281 (4) | 0.0199 (4) | −0.0015 (3) | 0.0071 (3) | 0.0021 (3) |
Ti1 | 0.02048 (11) | 0.01844 (11) | 0.01757 (11) | −0.00347 (7) | 0.00591 (8) | −0.00093 (6) |
Ti2 | 0.02010 (11) | 0.02133 (11) | 0.01558 (10) | 0.00042 (7) | 0.00478 (8) | −0.00092 (6) |
C1—C2 | 1.3133 (18) | C13—N2 | 1.4665 (14) |
C1—O1 | 1.3443 (14) | C13—C14 | 1.5198 (16) |
C1—H1 | 0.9500 | C13—C15 | 1.5267 (16) |
C2—H2A | 0.9500 | C13—H13 | 1.0000 |
C2—H2B | 0.9500 | C14—H14A | 0.9800 |
C3—N1 | 1.4703 (14) | C14—H14B | 0.9800 |
C3—C4 | 1.5124 (17) | C14—H14C | 0.9800 |
C3—C5 | 1.5197 (17) | C15—H15A | 0.9800 |
C3—H3 | 1.0000 | C15—H15B | 0.9800 |
C4—H4A | 0.9800 | C15—H15C | 0.9800 |
C4—H4B | 0.9800 | C16—C20 | 1.4028 (18) |
C4—H4C | 0.9800 | C16—C17 | 1.4118 (19) |
C5—H5A | 0.9800 | C16—Ti2 | 2.3617 (12) |
C5—H5B | 0.9800 | C16—H16 | 0.9500 |
C5—H5C | 0.9800 | C17—C18 | 1.3963 (19) |
C6—C7 | 1.4039 (17) | C17—Ti2 | 2.3869 (12) |
C6—C10 | 1.4155 (16) | C17—H17 | 0.9500 |
C6—Ti1 | 2.4096 (11) | C18—C19 | 1.3986 (18) |
C6—H6 | 0.9500 | C18—Ti2 | 2.4262 (11) |
C7—C8 | 1.4093 (18) | C18—H18 | 0.9500 |
C7—Ti1 | 2.4140 (12) | C19—C20 | 1.4158 (16) |
C7—H7 | 0.9500 | C19—Ti2 | 2.4087 (11) |
C8—C9 | 1.4071 (17) | C19—H19 | 0.9500 |
C8—Ti1 | 2.3878 (11) | C20—Ti2 | 2.3773 (12) |
C8—H8 | 0.9500 | C20—H20 | 0.9500 |
C9—C10 | 1.4094 (16) | N1—Ti1i | 1.8296 (9) |
C9—Ti1 | 2.3706 (11) | N1—Ti1 | 1.9972 (10) |
C9—H9 | 0.9500 | N2—Ti2ii | 1.8864 (9) |
C10—Ti1 | 2.3801 (11) | N2—Ti2 | 1.9398 (9) |
C10—H10 | 0.9500 | O1—Ti1 | 1.8834 (8) |
C11—C12 | 1.315 (2) | O2—Ti2 | 1.8913 (8) |
C11—O2 | 1.3395 (16) | Ti1—N1i | 1.8296 (9) |
C11—H11 | 0.9500 | Ti1—Ti1i | 2.7725 (4) |
C12—H12A | 0.9500 | Ti2—N2ii | 1.8864 (9) |
C12—H12B | 0.9500 | Ti2—Ti2ii | 2.8022 (4) |
C2—C1—O1 | 124.77 (11) | C19—C18—H18 | 125.9 |
C2—C1—H1 | 117.6 | Ti2—C18—H18 | 121.7 |
O1—C1—H1 | 117.6 | C18—C19—C20 | 108.23 (11) |
C1—C2—H2A | 120.0 | C18—C19—Ti2 | 73.87 (7) |
C1—C2—H2B | 120.0 | C20—C19—Ti2 | 71.58 (7) |
H2A—C2—H2B | 120.0 | C18—C19—H19 | 125.9 |
N1—C3—C4 | 109.44 (10) | C20—C19—H19 | 125.9 |
N1—C3—C5 | 112.22 (9) | Ti2—C19—H19 | 120.4 |
C4—C3—C5 | 111.57 (10) | C16—C20—C19 | 107.48 (11) |
N1—C3—H3 | 107.8 | C16—C20—Ti2 | 72.18 (7) |
C4—C3—H3 | 107.8 | C19—C20—Ti2 | 74.01 (7) |
C5—C3—H3 | 107.8 | C16—C20—H20 | 126.3 |
C3—C4—H4A | 109.5 | C19—C20—H20 | 126.3 |
C3—C4—H4B | 109.5 | Ti2—C20—H20 | 119.4 |
H4A—C4—H4B | 109.5 | C3—N1—Ti1i | 151.07 (8) |
C3—C4—H4C | 109.5 | C3—N1—Ti1 | 114.31 (7) |
H4A—C4—H4C | 109.5 | Ti1i—N1—Ti1 | 92.75 (4) |
H4B—C4—H4C | 109.5 | C13—N2—Ti2ii | 133.70 (7) |
C3—C5—H5A | 109.5 | C13—N2—Ti2 | 129.43 (7) |
C3—C5—H5B | 109.5 | Ti2ii—N2—Ti2 | 94.16 (4) |
H5A—C5—H5B | 109.5 | C1—O1—Ti1 | 131.09 (7) |
C3—C5—H5C | 109.5 | C11—O2—Ti2 | 129.76 (8) |
H5A—C5—H5C | 109.5 | N1i—Ti1—O1 | 106.79 (4) |
H5B—C5—H5C | 109.5 | N1i—Ti1—N1 | 87.25 (4) |
C7—C6—C10 | 107.71 (10) | O1—Ti1—N1 | 101.68 (4) |
C7—C6—Ti1 | 73.25 (6) | N1i—Ti1—C9 | 93.65 (4) |
C10—C6—Ti1 | 71.67 (6) | O1—Ti1—C9 | 142.01 (4) |
C7—C6—H6 | 126.1 | N1—Ti1—C9 | 111.16 (4) |
C10—C6—H6 | 126.1 | N1i—Ti1—C10 | 121.55 (4) |
Ti1—C6—H6 | 120.7 | O1—Ti1—C10 | 130.56 (4) |
C6—C7—C8 | 108.34 (11) | N1—Ti1—C10 | 90.95 (4) |
C6—C7—Ti1 | 72.91 (7) | C9—Ti1—C10 | 34.52 (4) |
C8—C7—Ti1 | 71.91 (7) | N1i—Ti1—C8 | 97.76 (4) |
C6—C7—H7 | 125.8 | O1—Ti1—C8 | 109.60 (4) |
C8—C7—H7 | 125.8 | N1—Ti1—C8 | 145.17 (4) |
Ti1—C7—H7 | 121.1 | C9—Ti1—C8 | 34.40 (4) |
C9—C8—C7 | 107.98 (10) | C10—Ti1—C8 | 57.08 (4) |
C9—C8—Ti1 | 72.13 (6) | N1i—Ti1—C6 | 150.56 (4) |
C7—C8—Ti1 | 73.96 (7) | O1—Ti1—C6 | 96.60 (4) |
C9—C8—H8 | 126.0 | N1—Ti1—C6 | 105.55 (4) |
C7—C8—H8 | 126.0 | C9—Ti1—C6 | 57.12 (4) |
Ti1—C8—H8 | 119.7 | C10—Ti1—C6 | 34.37 (4) |
C8—C9—C10 | 107.96 (10) | C8—Ti1—C6 | 56.77 (4) |
C8—C9—Ti1 | 73.47 (6) | N1i—Ti1—C7 | 129.22 (4) |
C10—C9—Ti1 | 73.11 (6) | O1—Ti1—C7 | 85.81 (4) |
C8—C9—H9 | 126.0 | N1—Ti1—C7 | 139.30 (4) |
C10—C9—H9 | 126.0 | C9—Ti1—C7 | 56.86 (4) |
Ti1—C9—H9 | 119.3 | C10—Ti1—C7 | 56.70 (4) |
C9—C10—C6 | 108.01 (10) | C8—Ti1—C7 | 34.13 (4) |
C9—C10—Ti1 | 72.37 (6) | C6—Ti1—C7 | 33.84 (4) |
C6—C10—Ti1 | 73.96 (6) | N1i—Ti1—Ti1i | 46.02 (3) |
C9—C10—H10 | 126.0 | O1—Ti1—Ti1i | 109.66 (3) |
C6—C10—H10 | 126.0 | N1—Ti1—Ti1i | 41.24 (3) |
Ti1—C10—H10 | 119.5 | C9—Ti1—Ti1i | 107.58 (3) |
C12—C11—O2 | 124.91 (14) | C10—Ti1—Ti1i | 110.93 (3) |
C12—C11—H11 | 117.5 | C8—Ti1—Ti1i | 132.88 (3) |
O2—C11—H11 | 117.5 | C6—Ti1—Ti1i | 140.16 (3) |
C11—C12—H12A | 120.0 | C7—Ti1—Ti1i | 164.44 (3) |
C11—C12—H12B | 120.0 | N2ii—Ti2—O2 | 107.20 (4) |
H12A—C12—H12B | 120.0 | N2ii—Ti2—N2 | 85.84 (4) |
N2—C13—C14 | 109.58 (9) | O2—Ti2—N2 | 103.11 (4) |
N2—C13—C15 | 113.45 (9) | N2ii—Ti2—C16 | 117.65 (4) |
C14—C13—C15 | 110.07 (10) | O2—Ti2—C16 | 131.96 (4) |
N2—C13—H13 | 107.9 | N2—Ti2—C16 | 96.63 (4) |
C14—C13—H13 | 107.9 | N2ii—Ti2—C20 | 88.59 (4) |
C15—C13—H13 | 107.9 | O2—Ti2—C20 | 140.36 (4) |
C13—C14—H14A | 109.5 | N2—Ti2—C20 | 114.35 (4) |
C13—C14—H14B | 109.5 | C16—Ti2—C20 | 34.43 (5) |
H14A—C14—H14B | 109.5 | N2ii—Ti2—C17 | 145.09 (4) |
C13—C14—H14C | 109.5 | O2—Ti2—C17 | 97.53 (4) |
H14A—C14—H14C | 109.5 | N2—Ti2—C17 | 112.49 (4) |
H14B—C14—H14C | 109.5 | C16—Ti2—C17 | 34.59 (5) |
C13—C15—H15A | 109.5 | C20—Ti2—C17 | 57.08 (5) |
C13—C15—H15B | 109.5 | N2ii—Ti2—C19 | 92.34 (4) |
H15A—C15—H15B | 109.5 | O2—Ti2—C19 | 107.19 (4) |
C13—C15—H15C | 109.5 | N2—Ti2—C19 | 148.75 (4) |
H15A—C15—H15C | 109.5 | C16—Ti2—C19 | 56.89 (4) |
H15B—C15—H15C | 109.5 | C20—Ti2—C19 | 34.41 (4) |
C20—C16—C17 | 107.95 (11) | C17—Ti2—C19 | 56.31 (4) |
C20—C16—Ti2 | 73.39 (7) | N2ii—Ti2—C18 | 123.60 (4) |
C17—C16—Ti2 | 73.68 (7) | O2—Ti2—C18 | 85.03 (4) |
C20—C16—H16 | 126.0 | N2—Ti2—C18 | 146.12 (4) |
C17—C16—H16 | 126.0 | C16—Ti2—C18 | 56.71 (4) |
Ti2—C16—H16 | 118.8 | C20—Ti2—C18 | 56.67 (4) |
C18—C17—C16 | 108.20 (11) | C17—Ti2—C18 | 33.72 (5) |
C18—C17—Ti2 | 74.68 (7) | C19—Ti2—C18 | 33.63 (4) |
C16—C17—Ti2 | 71.73 (7) | N2ii—Ti2—Ti2ii | 43.66 (3) |
C18—C17—H17 | 125.9 | O2—Ti2—Ti2ii | 110.86 (3) |
C16—C17—H17 | 125.9 | N2—Ti2—Ti2ii | 42.18 (3) |
Ti2—C17—H17 | 119.5 | C16—Ti2—Ti2ii | 113.10 (3) |
C17—C18—C19 | 108.13 (11) | C20—Ti2—Ti2ii | 105.60 (3) |
C17—C18—Ti2 | 71.60 (7) | C17—Ti2—Ti2ii | 144.77 (4) |
C19—C18—Ti2 | 72.50 (7) | C19—Ti2—Ti2ii | 128.26 (3) |
C17—C18—H18 | 125.9 | C18—Ti2—Ti2ii | 161.30 (3) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ti2(C5H5)2(C3H7N)2(C2H3O)2] |
Mr | 426.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 13.8746 (4), 9.7484 (2), 16.3264 (4) |
β (°) | 106.593 (2) |
V (Å3) | 2116.27 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.50 × 0.40 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDS II |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32869, 4625, 4211 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.069, 1.05 |
No. of reflections | 4625 |
No. of parameters | 239 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.37 |
Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
References
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The reaction of Cp2TiCl2, n-butyllithium and isopropylamine in THF was investigated to synthesize the new titanocene imido compound Cp2Ti=N-iPr. However, the excess of n-butyllithium led to THF cleavage, involving the formation of vinyloxy species. Substitution of one of the Cp ligands by the vinyloxy ligand was observed, together with the imido unit bridging over two titanium centers, thus forming a dinuclear complex. The asymmetric unit contains two half molecules of the title compound. Each titanium center is coordinated by one Cp ligand, one vinyloxy unit and two bridging imido groups (Fig. 1). The geometry at the titanium centers is strongly distorted tetrahedral. The largest deviation from the ideal tetrahedral angle is observed for N2—Ti2—N2A with 85.84 (4)°. The central four-membered metallacycles Ti1, N1, Ti1A, N1A and Ti2, N2, Ti2A, N2A are planar by virtue of the inversion symmetry.