Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010101592X/fr1316sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010101592X/fr1316Isup2.hkl |
CCDC reference: 179262
For related literature, see: Abboud et al. (1997); Dahlmann et al. (2000); Devore et al. (1995); Erker et al. (1985); Lappert et al. (1980); McKnight & Waymouth (1998); Stevens et al. (1991); Yasuda et al. (1985).
Me2Si(η5-2,3,4,6-Me4C9H2)(C4H7N)Ti(1,4-Ph2C4H4) was prepared from the reaction of Me2Si(η5-2,3,4,6-Me4C9H2)(C4H7N)TiCl2 with two equivalents of nBuMgBr in the presence of one equivalent of trans-1,4-diphenyl-1,3-butadiene in hexanes under inert atomospheric conditions, using a similar procedure to that described previously by Devore et al. (1995). The resulting dark-red solution was stored at 238 K in a glove-box for 5 d, after which time, dark crystals of the title complex had formed. The selected crystal was immersed in Paratone N oil and mounted on a thin glass fiber in a glove-box.
C—H distances of 0.98 and 0.99 Å were used for methyl and secondary H atoms, respectively. A distance of 0.95 Å was used for H atoms on Csp2 atoms. The H-atom displacement parameters were set at 1.2Ueq (1.5Ueq for the methyl H atoms) of the parent C atom. The H atoms on atoms C20—C23, as well as the methyl H atoms on C10 and C11, were obtained from a difference Fourier map and refined without any constraints [C—H = 0.93 (2)–1.02 (3) Å]. Full data collection details are in the relevant _special_details section of the archived CIF and also reported elsewhere (Abboud et al., 1997).
Data collection: SMART (Bruker, 1998); cell refinement: SMART and SAINT (Bruker, 1998); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), with 50% probability ellipsoids, showing the atom-numbering scheme. |
[Ti(C19H27NSi)(C16H14)] | F(000) = 1176 |
Mr = 551.68 | Dx = 1.249 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0726 (6) Å | Cell parameters from 4542 reflections |
b = 20.509 (1) Å | θ = 2.0–27.5° |
c = 13.9311 (8) Å | µ = 0.36 mm−1 |
β = 112.020 (1)° | T = 173 K |
V = 2932.9 (3) Å3 | Needle, black |
Z = 4 | 0.19 × 0.15 × 0.09 mm |
Bruker SMART diffractometer | 6740 independent reflections |
Radiation source: normal-focus sealed tube | 4070 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: analytical integration, based on measured indexed faces (SHELXTL; Sheldrick, 1998) | h = −14→13 |
Tmin = 0.931, Tmax = 0.973 | k = −26→15 |
20107 measured reflections | l = −17→18 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0458P)2] where P = (Fo2 + 2Fc2)/3 |
6740 reflections | (Δ/σ)max = 0.007 |
383 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Ti(C19H27NSi)(C16H14)] | V = 2932.9 (3) Å3 |
Mr = 551.68 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0726 (6) Å | µ = 0.36 mm−1 |
b = 20.509 (1) Å | T = 173 K |
c = 13.9311 (8) Å | 0.19 × 0.15 × 0.09 mm |
β = 112.020 (1)° |
Bruker SMART diffractometer | 6740 independent reflections |
Absorption correction: analytical integration, based on measured indexed faces (SHELXTL; Sheldrick, 1998) | 4070 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.973 | Rint = 0.055 |
20107 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.103 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.32 e Å−3 |
6740 reflections | Δρmin = −0.31 e Å−3 |
383 parameters |
Experimental. All syntheses and manipulations of air-sensitive materials were carried out in an inert atmosphere (argon) glove box. Solvents were first saturated with nitrogen and then dried by passage through activated alumina and Q-5TM catalyst prior to use. Deuterated NMR solvents were dried over sodium/potassium alloy and distilled and/or filtered prior to use. A Bruker SMART PLATFORM with a CCD area detector was used for data collection. The selected crystal was mounted on a thin glass fiber and bathed in a cold nitrogen stream for the duration of this study. A hemisphere of frames, 0.3° in ω, was collected. The first 50 frames were remeasured at the end of data collection to monitor instrument and crystal stability. Three sets of 20 frames were collected covering three perpendicular sectors of space. Reflections from these frames were used to obtain an initial set of cell parameters. 1381 frames, 0.3° in ω, were measured in three separate runs. This provided a range of at least 2.4 to 3.6 redundancy level. The first 50 frames were remeasured at the end of data collections in order to monitor crystal and instrument stability and to enable crystal decay corrections. This procedure is different from using standardreflections as with conventional diffractometers. Thus the CIF items -diffrn-standards-number, -diffrn-standards-interval-time and -diffrn-standards-interval-time are neither produced nor needed. Program SAINT was used to integrate all frames and 8192 reflections were used to refine the cell 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 | ||
Ti | 0.54291 (4) | 0.272935 (19) | 0.63494 (3) | 0.02444 (11) | |
Si | 0.53023 (6) | 0.19255 (3) | 0.79841 (5) | 0.02882 (16) | |
N1 | 0.42767 (17) | 0.21588 (8) | 0.67538 (13) | 0.0254 (4) | |
C1 | 0.6683 (2) | 0.24417 (11) | 0.79705 (16) | 0.0281 (5) | |
C2 | 0.7466 (2) | 0.22813 (12) | 0.73696 (17) | 0.0341 (6) | |
C3 | 0.7827 (2) | 0.28541 (13) | 0.70004 (18) | 0.0365 (6) | |
C4 | 0.7465 (3) | 0.40900 (13) | 0.73082 (19) | 0.0430 (7) | |
C5 | 0.6883 (3) | 0.44781 (13) | 0.7797 (2) | 0.0459 (7) | |
H5A | 0.6986 | 0.4937 | 0.7767 | 0.055* | |
C6 | 0.6125 (2) | 0.42359 (12) | 0.83547 (18) | 0.0385 (6) | |
C7 | 0.6001 (2) | 0.35835 (11) | 0.84316 (17) | 0.0304 (5) | |
H7A | 0.5481 | 0.3418 | 0.8785 | 0.037* | |
C8 | 0.6640 (2) | 0.31427 (11) | 0.79906 (15) | 0.0271 (5) | |
C9 | 0.7346 (2) | 0.34012 (12) | 0.73911 (17) | 0.0321 (5) | |
C10 | 0.4731 (3) | 0.21363 (16) | 0.9048 (2) | 0.0404 (7) | |
H10A | 0.432 (2) | 0.2551 (12) | 0.8964 (17) | 0.032 (7)* | |
H10B | 0.416 (3) | 0.1807 (14) | 0.911 (2) | 0.067 (9)* | |
H10C | 0.551 (3) | 0.2130 (13) | 0.973 (2) | 0.071 (9)* | |
C11 | 0.5712 (3) | 0.10433 (14) | 0.8134 (2) | 0.0454 (7) | |
H11A | 0.566 (3) | 0.0842 (13) | 0.748 (2) | 0.058 (8)* | |
H11B | 0.509 (3) | 0.0803 (13) | 0.8317 (19) | 0.051 (8)* | |
H11C | 0.651 (3) | 0.0983 (12) | 0.867 (2) | 0.048 (8)* | |
C12 | 0.2939 (2) | 0.19578 (11) | 0.62254 (16) | 0.0278 (5) | |
H12A | 0.2614 | 0.2139 | 0.5507 | 0.033* | |
C13 | 0.2535 (2) | 0.12358 (11) | 0.61712 (19) | 0.0398 (6) | |
H13A | 0.2426 | 0.1021 | 0.5507 | 0.048* | |
H13B | 0.3094 | 0.0972 | 0.6768 | 0.048* | |
C14 | 0.1250 (3) | 0.14548 (14) | 0.6249 (2) | 0.0494 (7) | |
H14A | 0.0522 | 0.1502 | 0.5572 | 0.059* | |
H14B | 0.0986 | 0.1190 | 0.6733 | 0.059* | |
C15 | 0.1916 (2) | 0.20993 (13) | 0.6710 (2) | 0.0445 (7) | |
H15A | 0.2279 | 0.2109 | 0.7476 | 0.053* | |
H15B | 0.1375 | 0.2490 | 0.6422 | 0.053* | |
C16 | 0.7869 (3) | 0.16054 (13) | 0.7182 (2) | 0.0490 (7) | |
H16A | 0.8745 | 0.1512 | 0.7686 | 0.074* | |
H16B | 0.7871 | 0.1580 | 0.6480 | 0.074* | |
H16C | 0.7253 | 0.1286 | 0.7257 | 0.074* | |
C17 | 0.8739 (3) | 0.28722 (15) | 0.6413 (2) | 0.0578 (9) | |
H17A | 0.9638 | 0.2927 | 0.6904 | 0.087* | |
H17B | 0.8502 | 0.3238 | 0.5925 | 0.087* | |
H17C | 0.8665 | 0.2463 | 0.6032 | 0.087* | |
C18 | 0.8238 (3) | 0.43774 (15) | 0.6716 (2) | 0.0673 (9) | |
H18A | 0.8210 | 0.4854 | 0.6745 | 0.101* | |
H18B | 0.7861 | 0.4234 | 0.5993 | 0.101* | |
H18C | 0.9144 | 0.4230 | 0.7027 | 0.101* | |
C19 | 0.5455 (3) | 0.47112 (13) | 0.8818 (2) | 0.0532 (8) | |
H19A | 0.4977 | 0.4470 | 0.9171 | 0.080* | |
H19B | 0.4846 | 0.4980 | 0.8267 | 0.080* | |
H19C | 0.6108 | 0.4992 | 0.9317 | 0.080* | |
C20 | 0.5099 (2) | 0.23085 (12) | 0.48052 (16) | 0.0291 (5) | |
H20 | 0.422 (2) | 0.2268 (10) | 0.4684 (16) | 0.028 (6)* | |
C21 | 0.5469 (2) | 0.29640 (12) | 0.47512 (17) | 0.0318 (6) | |
H21 | 0.626 (2) | 0.3056 (10) | 0.4642 (17) | 0.035 (6)* | |
C22 | 0.4970 (2) | 0.35083 (12) | 0.50795 (17) | 0.0325 (6) | |
H22 | 0.548 (2) | 0.3904 (11) | 0.5134 (16) | 0.027 (6)* | |
C23 | 0.3999 (2) | 0.35019 (12) | 0.55152 (16) | 0.0290 (5) | |
H23 | 0.336 (2) | 0.3140 (10) | 0.5279 (16) | 0.029 (6)* | |
C24 | 0.5698 (2) | 0.17466 (12) | 0.44952 (16) | 0.0306 (5) | |
C25 | 0.5279 (3) | 0.11183 (13) | 0.45826 (19) | 0.0434 (7) | |
H25A | 0.4601 | 0.1058 | 0.4836 | 0.052* | |
C26 | 0.5828 (3) | 0.05788 (13) | 0.4310 (2) | 0.0512 (7) | |
H26A | 0.5530 | 0.0155 | 0.4386 | 0.061* | |
C27 | 0.6804 (3) | 0.06510 (14) | 0.3927 (2) | 0.0495 (7) | |
H27A | 0.7184 | 0.0280 | 0.3743 | 0.059* | |
C28 | 0.7218 (3) | 0.12687 (13) | 0.3816 (2) | 0.0480 (7) | |
H28A | 0.7884 | 0.1326 | 0.3549 | 0.058* | |
C29 | 0.6668 (3) | 0.18069 (13) | 0.40919 (19) | 0.0407 (6) | |
H29A | 0.6962 | 0.2230 | 0.4004 | 0.049* | |
C30 | 0.3498 (2) | 0.40971 (11) | 0.58318 (16) | 0.0304 (5) | |
C31 | 0.2370 (3) | 0.40653 (13) | 0.60537 (19) | 0.0419 (6) | |
H31A | 0.1963 | 0.3655 | 0.6030 | 0.050* | |
C32 | 0.1830 (3) | 0.46159 (15) | 0.6307 (2) | 0.0502 (7) | |
H32A | 0.1051 | 0.4581 | 0.6440 | 0.060* | |
C33 | 0.2417 (3) | 0.52136 (13) | 0.6367 (2) | 0.0480 (7) | |
H33A | 0.2047 | 0.5592 | 0.6539 | 0.058* | |
C34 | 0.3542 (3) | 0.52577 (13) | 0.61760 (19) | 0.0449 (7) | |
H34A | 0.3958 | 0.5668 | 0.6227 | 0.054* | |
C35 | 0.4078 (2) | 0.47088 (12) | 0.59091 (18) | 0.0376 (6) | |
H35A | 0.4856 | 0.4750 | 0.5776 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0222 (2) | 0.0287 (2) | 0.0222 (2) | −0.00113 (18) | 0.00805 (15) | −0.00125 (17) |
Si | 0.0308 (4) | 0.0266 (4) | 0.0263 (3) | −0.0003 (3) | 0.0075 (3) | 0.0019 (3) |
N1 | 0.0239 (10) | 0.0261 (11) | 0.0252 (9) | 0.0000 (8) | 0.0081 (8) | −0.0006 (7) |
C1 | 0.0245 (13) | 0.0317 (14) | 0.0231 (11) | 0.0020 (10) | 0.0031 (9) | −0.0011 (9) |
C2 | 0.0234 (12) | 0.0441 (16) | 0.0291 (12) | 0.0040 (11) | 0.0033 (10) | −0.0049 (11) |
C3 | 0.0213 (13) | 0.0543 (18) | 0.0331 (13) | −0.0021 (11) | 0.0091 (10) | −0.0061 (11) |
C4 | 0.0432 (16) | 0.0444 (17) | 0.0371 (14) | −0.0204 (13) | 0.0100 (12) | −0.0015 (12) |
C5 | 0.0526 (18) | 0.0266 (15) | 0.0467 (16) | −0.0118 (12) | 0.0049 (14) | −0.0013 (12) |
C6 | 0.0416 (16) | 0.0342 (16) | 0.0307 (13) | 0.0027 (12) | 0.0032 (11) | −0.0065 (11) |
C7 | 0.0320 (14) | 0.0288 (14) | 0.0281 (12) | −0.0008 (10) | 0.0086 (10) | −0.0012 (10) |
C8 | 0.0227 (12) | 0.0326 (14) | 0.0211 (11) | −0.0025 (10) | 0.0026 (9) | −0.0043 (9) |
C9 | 0.0225 (13) | 0.0403 (15) | 0.0290 (12) | −0.0080 (10) | 0.0047 (10) | −0.0028 (10) |
C10 | 0.0462 (17) | 0.046 (2) | 0.0306 (14) | −0.0092 (14) | 0.0157 (13) | 0.0013 (12) |
C11 | 0.0436 (19) | 0.0329 (17) | 0.0489 (18) | 0.0027 (13) | 0.0049 (15) | 0.0076 (13) |
C12 | 0.0255 (13) | 0.0321 (13) | 0.0243 (11) | −0.0031 (10) | 0.0076 (9) | 0.0014 (9) |
C13 | 0.0426 (16) | 0.0318 (15) | 0.0367 (14) | −0.0080 (11) | 0.0053 (12) | 0.0051 (11) |
C14 | 0.0367 (16) | 0.067 (2) | 0.0430 (15) | −0.0186 (14) | 0.0135 (13) | 0.0071 (14) |
C15 | 0.0309 (15) | 0.066 (2) | 0.0389 (14) | −0.0062 (12) | 0.0154 (12) | −0.0090 (12) |
C16 | 0.0401 (17) | 0.0530 (19) | 0.0492 (16) | 0.0161 (13) | 0.0113 (13) | −0.0087 (13) |
C17 | 0.0306 (16) | 0.098 (3) | 0.0492 (17) | −0.0104 (15) | 0.0204 (13) | −0.0154 (16) |
C18 | 0.072 (2) | 0.068 (2) | 0.066 (2) | −0.0346 (18) | 0.0306 (18) | 0.0016 (16) |
C19 | 0.069 (2) | 0.0363 (17) | 0.0449 (16) | 0.0139 (14) | 0.0106 (15) | −0.0085 (12) |
C20 | 0.0258 (13) | 0.0366 (15) | 0.0245 (11) | −0.0007 (11) | 0.0091 (10) | −0.0021 (10) |
C21 | 0.0327 (14) | 0.0399 (16) | 0.0249 (12) | −0.0006 (11) | 0.0133 (10) | −0.0006 (10) |
C22 | 0.0357 (15) | 0.0334 (15) | 0.0284 (12) | −0.0022 (11) | 0.0119 (11) | 0.0014 (10) |
C23 | 0.0319 (14) | 0.0290 (14) | 0.0257 (12) | −0.0019 (11) | 0.0104 (10) | 0.0015 (10) |
C24 | 0.0320 (14) | 0.0358 (15) | 0.0234 (12) | 0.0012 (10) | 0.0098 (10) | −0.0020 (10) |
C25 | 0.0542 (18) | 0.0420 (17) | 0.0439 (15) | −0.0041 (13) | 0.0298 (14) | −0.0037 (12) |
C26 | 0.070 (2) | 0.0350 (17) | 0.0571 (18) | −0.0043 (14) | 0.0339 (16) | −0.0039 (13) |
C27 | 0.062 (2) | 0.0411 (18) | 0.0512 (17) | 0.0118 (14) | 0.0274 (15) | −0.0065 (13) |
C28 | 0.0477 (18) | 0.0471 (19) | 0.0601 (18) | 0.0005 (13) | 0.0330 (15) | −0.0097 (14) |
C29 | 0.0446 (16) | 0.0389 (16) | 0.0456 (15) | −0.0008 (12) | 0.0249 (13) | −0.0059 (12) |
C30 | 0.0341 (14) | 0.0323 (14) | 0.0244 (12) | 0.0025 (10) | 0.0104 (10) | 0.0017 (10) |
C31 | 0.0436 (17) | 0.0428 (17) | 0.0445 (15) | −0.0053 (12) | 0.0224 (13) | −0.0078 (12) |
C32 | 0.0469 (18) | 0.059 (2) | 0.0554 (18) | 0.0055 (14) | 0.0310 (15) | −0.0065 (14) |
C33 | 0.064 (2) | 0.0417 (18) | 0.0450 (16) | 0.0174 (14) | 0.0284 (15) | 0.0018 (13) |
C34 | 0.066 (2) | 0.0306 (16) | 0.0447 (16) | 0.0051 (13) | 0.0288 (15) | 0.0059 (12) |
C35 | 0.0443 (16) | 0.0353 (16) | 0.0386 (14) | 0.0053 (12) | 0.0217 (12) | 0.0059 (11) |
Ti—N1 | 1.963 (2) | C14—H14B | 0.9900 |
Ti—C20 | 2.217 (2) | C15—H15A | 0.9900 |
Ti—C23 | 2.233 (2) | C15—H15B | 0.9900 |
Ti—C1 | 2.242 (2) | C16—H16A | 0.9800 |
Ti—C21 | 2.295 (2) | C16—H16B | 0.9800 |
Ti—C22 | 2.295 (2) | C16—H16C | 0.9800 |
Ti—C8 | 2.334 (2) | C17—H17A | 0.9800 |
Ti—C2 | 2.355 (2) | C17—H17B | 0.9800 |
Ti—C3 | 2.476 (2) | C17—H17C | 0.9800 |
Ti—C9 | 2.490 (2) | C18—H18A | 0.9800 |
Ti—Si | 2.8572 (7) | C18—H18B | 0.9800 |
Si—N1 | 1.7311 (18) | C18—H18C | 0.9800 |
Si—C11 | 1.858 (3) | C19—H19A | 0.9800 |
Si—C1 | 1.865 (2) | C19—H19B | 0.9800 |
Si—C10 | 1.867 (3) | C19—H19C | 0.9800 |
N1—C12 | 1.445 (3) | C20—C21 | 1.416 (3) |
C1—C8 | 1.439 (3) | C20—C24 | 1.473 (3) |
C1—C2 | 1.451 (3) | C20—H20 | 0.93 (2) |
C2—C3 | 1.399 (3) | C21—C22 | 1.397 (3) |
C2—C16 | 1.509 (3) | C21—H21 | 0.96 (2) |
C3—C9 | 1.434 (3) | C22—C23 | 1.419 (3) |
C3—C17 | 1.520 (3) | C22—H22 | 0.98 (2) |
C4—C5 | 1.356 (4) | C23—C30 | 1.475 (3) |
C4—C9 | 1.428 (3) | C23—H23 | 0.99 (2) |
C4—C18 | 1.514 (4) | C24—C25 | 1.390 (3) |
C5—C6 | 1.430 (4) | C24—C29 | 1.393 (3) |
C5—H5A | 0.9500 | C25—C26 | 1.382 (3) |
C6—C7 | 1.353 (3) | C25—H25A | 0.9500 |
C6—C19 | 1.508 (3) | C26—C27 | 1.381 (4) |
C7—C8 | 1.422 (3) | C26—H26A | 0.9500 |
C7—H7A | 0.9500 | C27—C28 | 1.376 (4) |
C8—C9 | 1.441 (3) | C27—H27A | 0.9500 |
C10—H10A | 0.95 (2) | C28—C29 | 1.383 (3) |
C10—H10B | 0.95 (3) | C28—H28A | 0.9500 |
C10—H10C | 1.02 (3) | C29—H29A | 0.9500 |
C11—H11A | 0.98 (3) | C30—C31 | 1.396 (3) |
C11—H11B | 0.96 (3) | C30—C35 | 1.395 (3) |
C11—H11C | 0.92 (3) | C31—C32 | 1.384 (3) |
C12—C13 | 1.540 (3) | C31—H31A | 0.9500 |
C12—C15 | 1.548 (3) | C32—C33 | 1.375 (4) |
C12—H12A | 1.0000 | C32—H32A | 0.9500 |
C13—C14 | 1.534 (4) | C33—C34 | 1.370 (4) |
C13—H13A | 0.9900 | C33—H33A | 0.9500 |
C13—H13B | 0.9900 | C34—C35 | 1.387 (3) |
C14—C15 | 1.532 (4) | C34—H34A | 0.9500 |
C14—H14A | 0.9900 | C35—H35A | 0.9500 |
Cp—Ti—N1 | 110.40 (8) | H10B—C10—H10C | 106 (2) |
N1—Ti—C20 | 99.09 (8) | Si—C11—H11A | 112.4 (16) |
N1—Ti—C23 | 99.33 (8) | Si—C11—H11B | 111.1 (16) |
C20—Ti—C23 | 86.82 (8) | H11A—C11—H11B | 104 (2) |
N1—Ti—C1 | 77.16 (8) | Si—C11—H11C | 109.9 (15) |
C20—Ti—C1 | 133.59 (9) | H11A—C11—H11C | 113 (2) |
C23—Ti—C1 | 139.59 (8) | H11B—C11—H11C | 107 (2) |
N1—Ti—C21 | 130.89 (8) | N1—C12—C13 | 121.49 (19) |
C20—Ti—C21 | 36.52 (8) | N1—C12—C15 | 120.16 (18) |
C23—Ti—C21 | 67.30 (8) | C13—C12—C15 | 87.44 (18) |
C1—Ti—C21 | 143.40 (9) | N1—C12—H12A | 108.6 |
N1—Ti—C22 | 131.01 (8) | C13—C12—H12A | 108.6 |
C20—Ti—C22 | 67.34 (9) | C15—C12—H12A | 108.6 |
C23—Ti—C22 | 36.48 (8) | C14—C13—C12 | 88.56 (18) |
C1—Ti—C22 | 146.56 (9) | C14—C13—H13A | 113.9 |
C21—Ti—C22 | 35.44 (8) | C12—C13—H13A | 113.9 |
N1—Ti—C8 | 97.59 (7) | C14—C13—H13B | 113.9 |
C20—Ti—C8 | 156.50 (8) | C12—C13—H13B | 113.9 |
C23—Ti—C8 | 106.67 (8) | H13A—C13—H13B | 111.1 |
C1—Ti—C8 | 36.60 (8) | C15—C14—C13 | 88.21 (19) |
C21—Ti—C8 | 131.41 (8) | C15—C14—H14A | 113.9 |
C22—Ti—C8 | 112.47 (8) | C13—C14—H14A | 113.9 |
N1—Ti—C2 | 99.94 (8) | C15—C14—H14B | 113.9 |
C20—Ti—C2 | 101.88 (8) | C13—C14—H14B | 113.9 |
C23—Ti—C2 | 157.27 (9) | H14A—C14—H14B | 111.2 |
C1—Ti—C2 | 36.69 (8) | C14—C15—C12 | 88.37 (18) |
C21—Ti—C2 | 107.75 (9) | C14—C15—H15A | 113.9 |
C22—Ti—C2 | 128.47 (9) | C12—C15—H15A | 113.9 |
C8—Ti—C2 | 58.80 (8) | C14—C15—H15B | 113.9 |
N1—Ti—C3 | 132.80 (8) | C12—C15—H15B | 113.9 |
C20—Ti—C3 | 99.18 (8) | H15A—C15—H15B | 111.1 |
C23—Ti—C3 | 124.80 (9) | C2—C16—H16A | 109.5 |
C1—Ti—C3 | 58.95 (8) | C2—C16—H16B | 109.5 |
C21—Ti—C3 | 85.73 (8) | H16A—C16—H16B | 109.5 |
C22—Ti—C3 | 96.18 (9) | C2—C16—H16C | 109.5 |
C8—Ti—C3 | 57.33 (8) | H16A—C16—H16C | 109.5 |
C2—Ti—C3 | 33.56 (8) | H16B—C16—H16C | 109.5 |
N1—Ti—C9 | 131.79 (7) | C3—C17—H17A | 109.5 |
C20—Ti—C9 | 125.12 (8) | C3—C17—H17B | 109.5 |
C23—Ti—C9 | 101.16 (9) | H17A—C17—H17B | 109.5 |
C1—Ti—C9 | 59.19 (8) | C3—C17—H17C | 109.5 |
C21—Ti—C9 | 97.30 (8) | H17A—C17—H17C | 109.5 |
C22—Ti—C9 | 87.60 (8) | H17B—C17—H17C | 109.5 |
C8—Ti—C9 | 34.58 (7) | C4—C18—H18A | 109.5 |
C2—Ti—C9 | 56.64 (9) | C4—C18—H18B | 109.5 |
C3—Ti—C9 | 33.57 (8) | H18A—C18—H18B | 109.5 |
N1—Ti—Si | 36.48 (5) | C4—C18—H18C | 109.5 |
C20—Ti—Si | 120.61 (6) | H18A—C18—H18C | 109.5 |
C23—Ti—Si | 125.95 (6) | H18B—C18—H18C | 109.5 |
C1—Ti—Si | 40.72 (6) | C6—C19—H19A | 109.5 |
C21—Ti—Si | 156.78 (7) | C6—C19—H19B | 109.5 |
C22—Ti—Si | 162.42 (6) | H19A—C19—H19B | 109.5 |
C8—Ti—Si | 67.09 (6) | C6—C19—H19C | 109.5 |
C2—Ti—Si | 67.41 (6) | H19A—C19—H19C | 109.5 |
C3—Ti—Si | 97.70 (6) | H19B—C19—H19C | 109.5 |
C9—Ti—Si | 98.08 (6) | C21—C20—C24 | 123.8 (2) |
N1—Si—C11 | 114.99 (12) | C21—C20—Ti | 74.71 (13) |
N1—Si—C1 | 93.96 (9) | C24—C20—Ti | 131.35 (16) |
C11—Si—C1 | 112.79 (13) | C21—C20—H20 | 112.4 (13) |
N1—Si—C10 | 115.47 (12) | C24—C20—H20 | 115.7 (13) |
C11—Si—C10 | 106.09 (15) | Ti—C20—H20 | 89.5 (13) |
C1—Si—C10 | 113.56 (12) | C22—C21—C20 | 125.7 (2) |
N1—Si—Ti | 42.39 (6) | C22—C21—Ti | 72.29 (13) |
C11—Si—Ti | 124.66 (11) | C20—C21—Ti | 68.77 (12) |
C1—Si—Ti | 51.62 (6) | C22—C21—H21 | 113.0 (13) |
C10—Si—Ti | 129.16 (10) | C20—C21—H21 | 119.6 (13) |
C12—N1—Si | 126.30 (14) | Ti—C21—H21 | 123.0 (14) |
C12—N1—Ti | 132.56 (14) | C21—C22—C23 | 126.1 (2) |
Si—N1—Ti | 101.14 (9) | C21—C22—Ti | 72.27 (14) |
C8—C1—C2 | 105.59 (19) | C23—C22—Ti | 69.40 (13) |
C8—C1—Si | 122.26 (16) | C21—C22—H22 | 113.6 (13) |
C2—C1—Si | 123.12 (17) | C23—C22—H22 | 119.0 (12) |
C8—C1—Ti | 75.18 (12) | Ti—C22—H22 | 124.3 (12) |
C2—C1—Ti | 75.91 (12) | C22—C23—C30 | 123.4 (2) |
Si—C1—Ti | 87.66 (9) | C22—C23—Ti | 74.12 (14) |
C3—C2—C1 | 109.7 (2) | C30—C23—Ti | 134.78 (15) |
C3—C2—C16 | 124.3 (2) | C22—C23—H23 | 115.0 (12) |
C1—C2—C16 | 126.0 (2) | C30—C23—H23 | 114.8 (13) |
C3—C2—Ti | 77.98 (14) | Ti—C23—H23 | 85.3 (13) |
C1—C2—Ti | 67.40 (12) | C25—C24—C29 | 116.8 (2) |
C16—C2—Ti | 122.17 (16) | C25—C24—C20 | 119.9 (2) |
C2—C3—C9 | 108.6 (2) | C29—C24—C20 | 123.3 (2) |
C2—C3—C17 | 123.9 (2) | C26—C25—C24 | 121.5 (2) |
C9—C3—C17 | 127.0 (2) | C26—C25—H25A | 119.2 |
C2—C3—Ti | 68.46 (13) | C24—C25—H25A | 119.2 |
C9—C3—Ti | 73.74 (13) | C27—C26—C25 | 120.6 (3) |
C17—C3—Ti | 130.00 (17) | C27—C26—H26A | 119.7 |
C5—C4—C9 | 117.7 (2) | C25—C26—H26A | 119.7 |
C5—C4—C18 | 121.1 (3) | C28—C27—C26 | 119.0 (2) |
C9—C4—C18 | 121.2 (3) | C28—C27—H27A | 120.5 |
C4—C5—C6 | 123.7 (2) | C26—C27—H27A | 120.5 |
C4—C5—H5A | 118.2 | C27—C28—C29 | 120.3 (2) |
C6—C5—H5A | 118.2 | C27—C28—H28A | 119.9 |
C7—C6—C5 | 118.9 (2) | C29—C28—H28A | 119.9 |
C7—C6—C19 | 121.6 (2) | C28—C29—C24 | 121.9 (2) |
C5—C6—C19 | 119.4 (2) | C28—C29—H29A | 119.1 |
C6—C7—C8 | 120.8 (2) | C24—C29—H29A | 119.1 |
C6—C7—H7A | 119.6 | C31—C30—C35 | 116.7 (2) |
C8—C7—H7A | 119.6 | C31—C30—C23 | 119.7 (2) |
C7—C8—C1 | 132.0 (2) | C35—C30—C23 | 123.6 (2) |
C7—C8—C9 | 118.8 (2) | C32—C31—C30 | 121.8 (2) |
C1—C8—C9 | 109.10 (19) | C32—C31—H31A | 119.1 |
C7—C8—Ti | 117.26 (15) | C30—C31—H31A | 119.1 |
C1—C8—Ti | 68.22 (11) | C33—C32—C31 | 120.2 (3) |
C9—C8—Ti | 78.65 (12) | C33—C32—H32A | 119.9 |
C4—C9—C3 | 133.2 (2) | C31—C32—H32A | 119.9 |
C4—C9—C8 | 119.8 (2) | C34—C33—C32 | 119.4 (2) |
C3—C9—C8 | 106.9 (2) | C34—C33—H33A | 120.3 |
C4—C9—Ti | 125.78 (16) | C32—C33—H33A | 120.3 |
C3—C9—Ti | 72.69 (13) | C33—C34—C35 | 120.7 (3) |
C8—C9—Ti | 66.77 (12) | C33—C34—H34A | 119.7 |
Si—C10—H10A | 113.3 (13) | C35—C34—H34A | 119.7 |
Si—C10—H10B | 110.0 (16) | C34—C35—C30 | 121.3 (2) |
H10A—C10—H10B | 110 (2) | C34—C35—H35A | 119.4 |
Si—C10—H10C | 108.3 (16) | C30—C35—H35A | 119.4 |
H10A—C10—H10C | 109 (2) | ||
C20—Ti—Si—N1 | −60.56 (11) | C23—Ti—C8—C7 | 31.23 (19) |
C23—Ti—Si—N1 | 49.90 (11) | C1—Ti—C8—C7 | −127.2 (2) |
C1—Ti—Si—N1 | 176.71 (12) | C21—Ti—C8—C7 | 105.39 (18) |
C21—Ti—Si—N1 | −68.89 (19) | C22—Ti—C8—C7 | 69.56 (19) |
C22—Ti—Si—N1 | 52.1 (2) | C2—Ti—C8—C7 | −168.0 (2) |
C8—Ti—Si—N1 | 144.38 (10) | C3—Ti—C8—C7 | 152.3 (2) |
C2—Ti—Si—N1 | −151.30 (11) | C9—Ti—C8—C7 | 116.7 (2) |
C3—Ti—Si—N1 | −166.05 (10) | Si—Ti—C8—C7 | −91.37 (17) |
C9—Ti—Si—N1 | 160.05 (10) | N1—Ti—C8—C1 | 56.25 (13) |
N1—Ti—Si—C11 | 90.24 (15) | C20—Ti—C8—C1 | −78.7 (2) |
C20—Ti—Si—C11 | 29.69 (15) | C23—Ti—C8—C1 | 158.41 (13) |
C23—Ti—Si—C11 | 140.14 (15) | C21—Ti—C8—C1 | −127.43 (14) |
C1—Ti—Si—C11 | −93.05 (15) | C22—Ti—C8—C1 | −163.26 (13) |
C21—Ti—Si—C11 | 21.4 (2) | C2—Ti—C8—C1 | −40.81 (13) |
C22—Ti—Si—C11 | 142.3 (2) | C3—Ti—C8—C1 | −80.54 (14) |
C8—Ti—Si—C11 | −125.37 (14) | C9—Ti—C8—C1 | −116.08 (19) |
C2—Ti—Si—C11 | −61.05 (14) | Si—Ti—C8—C1 | 35.81 (11) |
C3—Ti—Si—C11 | −75.81 (14) | N1—Ti—C8—C9 | 172.34 (13) |
C9—Ti—Si—C11 | −109.71 (14) | C20—Ti—C8—C9 | 37.4 (3) |
N1—Ti—Si—C1 | −176.71 (12) | C23—Ti—C8—C9 | −85.51 (15) |
C20—Ti—Si—C1 | 122.73 (11) | C1—Ti—C8—C9 | 116.08 (19) |
C23—Ti—Si—C1 | −126.82 (12) | C21—Ti—C8—C9 | −11.35 (18) |
C21—Ti—Si—C1 | 114.40 (19) | C22—Ti—C8—C9 | −47.17 (16) |
C22—Ti—Si—C1 | −124.6 (2) | C2—Ti—C8—C9 | 75.28 (15) |
C8—Ti—Si—C1 | −32.33 (10) | C3—Ti—C8—C9 | 35.54 (13) |
C2—Ti—Si—C1 | 31.99 (11) | Si—Ti—C8—C9 | 151.89 (14) |
C3—Ti—Si—C1 | 17.24 (11) | C5—C4—C9—C3 | −179.2 (3) |
C9—Ti—Si—C1 | −16.66 (11) | C18—C4—C9—C3 | −0.6 (4) |
N1—Ti—Si—C10 | −86.00 (15) | C5—C4—C9—C8 | −0.8 (3) |
C20—Ti—Si—C10 | −146.56 (14) | C18—C4—C9—C8 | 177.8 (2) |
C23—Ti—Si—C10 | −36.11 (15) | C5—C4—C9—Ti | 80.7 (3) |
C1—Ti—Si—C10 | 90.71 (16) | C18—C4—C9—Ti | −100.6 (3) |
C21—Ti—Si—C10 | −154.9 (2) | C2—C3—C9—C4 | 176.9 (2) |
C22—Ti—Si—C10 | −33.9 (3) | C17—C3—C9—C4 | 5.0 (4) |
C8—Ti—Si—C10 | 58.38 (14) | Ti—C3—C9—C4 | −123.2 (3) |
C2—Ti—Si—C10 | 122.70 (14) | C2—C3—C9—C8 | −1.7 (3) |
C3—Ti—Si—C10 | 107.95 (14) | C17—C3—C9—C8 | −173.6 (2) |
C9—Ti—Si—C10 | 74.05 (14) | Ti—C3—C9—C8 | 58.21 (15) |
C11—Si—N1—C12 | 64.9 (2) | C2—C3—C9—Ti | −59.88 (16) |
C1—Si—N1—C12 | −177.70 (18) | C17—C3—C9—Ti | 128.2 (2) |
C10—Si—N1—C12 | −59.2 (2) | C7—C8—C9—C4 | 4.2 (3) |
Ti—Si—N1—C12 | 179.7 (2) | C1—C8—C9—C4 | −178.9 (2) |
C11—Si—N1—Ti | −114.85 (13) | Ti—C8—C9—C4 | 119.2 (2) |
C1—Si—N1—Ti | 2.58 (10) | C7—C8—C9—C3 | −177.04 (19) |
C10—Si—N1—Ti | 121.05 (12) | C1—C8—C9—C3 | −0.1 (2) |
C20—Ti—N1—C12 | −49.1 (2) | Ti—C8—C9—C3 | −62.03 (16) |
C23—Ti—N1—C12 | 39.2 (2) | C7—C8—C9—Ti | −115.01 (19) |
C1—Ti—N1—C12 | 178.1 (2) | C1—C8—C9—Ti | 61.96 (14) |
C21—Ti—N1—C12 | −28.8 (2) | N1—Ti—C9—C4 | −121.2 (2) |
C22—Ti—N1—C12 | 18.7 (2) | C20—Ti—C9—C4 | 86.3 (2) |
C8—Ti—N1—C12 | 147.55 (19) | C23—Ti—C9—C4 | −7.7 (2) |
C2—Ti—N1—C12 | −152.93 (19) | C1—Ti—C9—C4 | −149.5 (2) |
C3—Ti—N1—C12 | −160.68 (17) | C21—Ti—C9—C4 | 60.5 (2) |
C9—Ti—N1—C12 | 153.38 (17) | C22—Ti—C9—C4 | 26.3 (2) |
Si—Ti—N1—C12 | −179.7 (2) | C8—Ti—C9—C4 | −110.9 (3) |
C20—Ti—N1—Si | 130.62 (9) | C2—Ti—C9—C4 | 167.0 (2) |
C23—Ti—N1—Si | −141.14 (9) | C3—Ti—C9—C4 | 131.3 (3) |
C1—Ti—N1—Si | −2.20 (8) | Si—Ti—C9—C4 | −136.94 (19) |
C21—Ti—N1—Si | 150.89 (9) | N1—Ti—C9—C3 | 107.54 (15) |
C22—Ti—N1—Si | −161.58 (9) | C20—Ti—C9—C3 | −45.01 (17) |
C8—Ti—N1—Si | −32.76 (9) | C23—Ti—C9—C3 | −139.01 (14) |
C2—Ti—N1—Si | 26.76 (10) | C1—Ti—C9—C3 | 79.19 (15) |
C3—Ti—N1—Si | 19.00 (14) | C21—Ti—C9—C3 | −70.80 (15) |
C9—Ti—N1—Si | −26.93 (13) | C22—Ti—C9—C3 | −104.96 (14) |
N1—Si—C1—C8 | 68.60 (18) | C8—Ti—C9—C3 | 117.8 (2) |
C11—Si—C1—C8 | −172.16 (18) | C2—Ti—C9—C3 | 35.68 (13) |
C10—Si—C1—C8 | −51.4 (2) | Si—Ti—C9—C3 | 91.76 (13) |
Ti—Si—C1—C8 | 70.82 (16) | N1—Ti—C9—C8 | −10.21 (18) |
N1—Si—C1—C2 | −73.71 (19) | C20—Ti—C9—C8 | −162.77 (13) |
C11—Si—C1—C2 | 45.5 (2) | C23—Ti—C9—C8 | 103.24 (14) |
C10—Si—C1—C2 | 166.26 (19) | C1—Ti—C9—C8 | −38.57 (13) |
Ti—Si—C1—C2 | −71.49 (17) | C21—Ti—C9—C8 | 171.44 (14) |
N1—Si—C1—Ti | −2.22 (8) | C22—Ti—C9—C8 | 137.29 (14) |
C11—Si—C1—Ti | 117.01 (12) | C2—Ti—C9—C8 | −82.08 (15) |
C10—Si—C1—Ti | −122.25 (12) | C3—Ti—C9—C8 | −117.8 (2) |
N1—Ti—C1—C8 | −122.29 (13) | Si—Ti—C9—C8 | −25.99 (13) |
C20—Ti—C1—C8 | 147.33 (13) | Si—N1—C12—C13 | −48.5 (3) |
C23—Ti—C1—C8 | −32.94 (19) | Ti—N1—C12—C13 | 131.17 (19) |
C21—Ti—C1—C8 | 92.72 (17) | Si—N1—C12—C15 | 58.7 (3) |
C22—Ti—C1—C8 | 28.9 (2) | Ti—N1—C12—C15 | −121.6 (2) |
C2—Ti—C1—C8 | 110.67 (18) | N1—C12—C13—C14 | 144.5 (2) |
C3—Ti—C1—C8 | 75.75 (13) | C15—C12—C13—C14 | 20.30 (18) |
C9—Ti—C1—C8 | 36.41 (12) | C12—C13—C14—C15 | −20.5 (2) |
Si—Ti—C1—C8 | −124.29 (15) | C13—C14—C15—C12 | 20.40 (18) |
N1—Ti—C1—C2 | 127.04 (15) | N1—C12—C15—C14 | −145.7 (2) |
C20—Ti—C1—C2 | 36.66 (19) | C13—C12—C15—C14 | −20.34 (18) |
C23—Ti—C1—C2 | −143.61 (15) | N1—Ti—C20—C21 | 153.89 (14) |
C21—Ti—C1—C2 | −17.9 (2) | C23—Ti—C20—C21 | 54.94 (15) |
C22—Ti—C1—C2 | −81.8 (2) | C1—Ti—C20—C21 | −125.24 (15) |
C8—Ti—C1—C2 | −110.67 (18) | C22—Ti—C20—C21 | 23.09 (14) |
C3—Ti—C1—C2 | −34.92 (13) | C8—Ti—C20—C21 | −71.4 (3) |
C9—Ti—C1—C2 | −74.26 (14) | C2—Ti—C20—C21 | −103.86 (15) |
Si—Ti—C1—C2 | 125.03 (17) | C3—Ti—C20—C21 | −69.82 (15) |
N1—Ti—C1—Si | 2.00 (8) | C9—Ti—C20—C21 | −46.48 (17) |
C20—Ti—C1—Si | −88.37 (13) | Si—Ti—C20—C21 | −174.49 (12) |
C23—Ti—C1—Si | 91.36 (14) | N1—Ti—C20—C24 | −84.3 (2) |
C21—Ti—C1—Si | −142.98 (12) | C23—Ti—C20—C24 | 176.8 (2) |
C22—Ti—C1—Si | 153.18 (12) | C1—Ti—C20—C24 | −3.4 (3) |
C8—Ti—C1—Si | 124.29 (15) | C21—Ti—C20—C24 | 121.9 (3) |
C2—Ti—C1—Si | −125.03 (17) | C22—Ti—C20—C24 | 144.9 (2) |
C3—Ti—C1—Si | −159.95 (12) | C8—Ti—C20—C24 | 50.4 (3) |
C9—Ti—C1—Si | 160.70 (12) | C2—Ti—C20—C24 | 18.0 (2) |
C8—C1—C2—C3 | −2.7 (2) | C3—Ti—C20—C24 | 52.0 (2) |
Si—C1—C2—C3 | 144.79 (17) | C9—Ti—C20—C24 | 75.4 (2) |
Ti—C1—C2—C3 | 67.14 (17) | Si—Ti—C20—C24 | −52.6 (2) |
C8—C1—C2—C16 | 175.9 (2) | C24—C20—C21—C22 | −177.0 (2) |
Si—C1—C2—C16 | −36.6 (3) | Ti—C20—C21—C22 | −47.1 (2) |
Ti—C1—C2—C16 | −114.2 (2) | C24—C20—C21—Ti | −129.9 (2) |
C8—C1—C2—Ti | −69.89 (14) | N1—Ti—C21—C22 | 106.28 (16) |
Si—C1—C2—Ti | 77.65 (15) | C20—Ti—C21—C22 | 141.4 (2) |
N1—Ti—C2—C3 | −169.69 (13) | C23—Ti—C21—C22 | 23.74 (14) |
C20—Ti—C2—C3 | 88.74 (15) | C1—Ti—C21—C22 | −121.45 (17) |
C23—Ti—C2—C3 | −22.1 (3) | C8—Ti—C21—C22 | −68.88 (18) |
C1—Ti—C2—C3 | −117.5 (2) | C2—Ti—C21—C22 | −132.59 (15) |
C21—Ti—C2—C3 | 51.39 (15) | C3—Ti—C21—C22 | −106.93 (15) |
C22—Ti—C2—C3 | 18.35 (18) | C9—Ti—C21—C22 | −75.35 (15) |
C8—Ti—C2—C3 | −76.78 (14) | Si—Ti—C21—C22 | 153.47 (14) |
C9—Ti—C2—C3 | −35.69 (13) | N1—Ti—C21—C20 | −35.09 (18) |
Si—Ti—C2—C3 | −152.84 (15) | C23—Ti—C21—C20 | −117.63 (16) |
N1—Ti—C2—C1 | −52.20 (14) | C1—Ti—C21—C20 | 97.18 (18) |
C20—Ti—C2—C1 | −153.77 (14) | C22—Ti—C21—C20 | −141.4 (2) |
C23—Ti—C2—C1 | 95.4 (2) | C8—Ti—C21—C20 | 149.74 (14) |
C21—Ti—C2—C1 | 168.88 (14) | C2—Ti—C21—C20 | 86.03 (15) |
C22—Ti—C2—C1 | 135.84 (14) | C3—Ti—C21—C20 | 111.70 (15) |
C8—Ti—C2—C1 | 40.71 (13) | C9—Ti—C21—C20 | 143.28 (14) |
C3—Ti—C2—C1 | 117.5 (2) | Si—Ti—C21—C20 | 12.1 (3) |
C9—Ti—C2—C1 | 81.80 (14) | C20—C21—C22—C23 | −0.6 (4) |
Si—Ti—C2—C1 | −35.35 (12) | Ti—C21—C22—C23 | −46.4 (2) |
N1—Ti—C2—C16 | 67.2 (2) | C20—C21—C22—Ti | 45.8 (2) |
C20—Ti—C2—C16 | −34.4 (2) | N1—Ti—C22—C21 | −105.91 (16) |
C23—Ti—C2—C16 | −145.2 (2) | C20—Ti—C22—C21 | −23.74 (14) |
C1—Ti—C2—C16 | 119.4 (3) | C23—Ti—C22—C21 | −141.3 (2) |
C21—Ti—C2—C16 | −71.7 (2) | C1—Ti—C22—C21 | 112.62 (18) |
C22—Ti—C2—C16 | −104.8 (2) | C8—Ti—C22—C21 | 130.79 (14) |
C8—Ti—C2—C16 | 160.1 (2) | C2—Ti—C22—C21 | 63.58 (18) |
C3—Ti—C2—C16 | −123.1 (3) | C3—Ti—C22—C21 | 73.66 (15) |
C9—Ti—C2—C16 | −158.8 (2) | C9—Ti—C22—C21 | 106.16 (15) |
Si—Ti—C2—C16 | 84.0 (2) | Si—Ti—C22—C21 | −144.35 (19) |
C1—C2—C3—C9 | 2.8 (3) | N1—Ti—C22—C23 | 35.43 (18) |
C16—C2—C3—C9 | −175.9 (2) | C20—Ti—C22—C23 | 117.60 (16) |
Ti—C2—C3—C9 | 63.22 (16) | C1—Ti—C22—C23 | −106.03 (18) |
C1—C2—C3—C17 | 175.0 (2) | C21—Ti—C22—C23 | 141.3 (2) |
C16—C2—C3—C17 | −3.7 (4) | C8—Ti—C22—C23 | −87.87 (15) |
Ti—C2—C3—C17 | −124.6 (2) | C2—Ti—C22—C23 | −155.08 (14) |
C1—C2—C3—Ti | −60.44 (15) | C3—Ti—C22—C23 | −145.00 (14) |
C16—C2—C3—Ti | 120.9 (2) | C9—Ti—C22—C23 | −112.50 (15) |
N1—Ti—C3—C2 | 13.91 (18) | Si—Ti—C22—C23 | −3.0 (3) |
C20—Ti—C3—C2 | −97.67 (14) | C21—C22—C23—C30 | −179.0 (2) |
C23—Ti—C3—C2 | 169.81 (13) | Ti—C22—C23—C30 | 133.6 (2) |
C1—Ti—C3—C2 | 38.22 (13) | C21—C22—C23—Ti | 47.4 (2) |
C21—Ti—C3—C2 | −131.73 (15) | N1—Ti—C23—C22 | −153.68 (14) |
C22—Ti—C3—C2 | −165.65 (14) | C20—Ti—C23—C22 | −54.99 (15) |
C8—Ti—C3—C2 | 81.57 (15) | C1—Ti—C23—C22 | 125.21 (16) |
C9—Ti—C3—C2 | 118.2 (2) | C21—Ti—C23—C22 | −23.12 (14) |
Si—Ti—C3—C2 | 25.17 (14) | C8—Ti—C23—C22 | 105.43 (14) |
N1—Ti—C3—C9 | −104.30 (15) | C2—Ti—C23—C22 | 58.6 (3) |
C20—Ti—C3—C9 | 144.13 (14) | C3—Ti—C23—C22 | 43.99 (17) |
C23—Ti—C3—C9 | 51.61 (16) | C9—Ti—C23—C22 | 70.20 (15) |
C1—Ti—C3—C9 | −79.99 (14) | Si—Ti—C23—C22 | 178.88 (11) |
C21—Ti—C3—C9 | 110.06 (15) | N1—Ti—C23—C30 | 84.7 (2) |
C22—Ti—C3—C9 | 76.15 (14) | C20—Ti—C23—C30 | −176.6 (2) |
C8—Ti—C3—C9 | −36.63 (13) | C1—Ti—C23—C30 | 3.6 (3) |
C2—Ti—C3—C9 | −118.2 (2) | C21—Ti—C23—C30 | −144.8 (3) |
Si—Ti—C3—C9 | −93.03 (13) | C22—Ti—C23—C30 | −121.6 (3) |
N1—Ti—C3—C17 | 130.7 (2) | C8—Ti—C23—C30 | −16.2 (3) |
C20—Ti—C3—C17 | 19.2 (3) | C2—Ti—C23—C30 | −63.0 (3) |
C23—Ti—C3—C17 | −73.4 (3) | C3—Ti—C23—C30 | −77.6 (2) |
C1—Ti—C3—C17 | 155.0 (3) | C9—Ti—C23—C30 | −51.4 (2) |
C21—Ti—C3—C17 | −14.9 (2) | Si—Ti—C23—C30 | 57.2 (3) |
C22—Ti—C3—C17 | −48.8 (2) | C21—C20—C24—C25 | 179.5 (2) |
C8—Ti—C3—C17 | −161.6 (3) | Ti—C20—C24—C25 | 79.9 (3) |
C2—Ti—C3—C17 | 116.8 (3) | C21—C20—C24—C29 | −1.7 (3) |
C9—Ti—C3—C17 | −125.0 (3) | Ti—C20—C24—C29 | −101.3 (3) |
Si—Ti—C3—C17 | 142.0 (2) | C29—C24—C25—C26 | 1.8 (4) |
C9—C4—C5—C6 | −2.3 (4) | C20—C24—C25—C26 | −179.3 (2) |
C18—C4—C5—C6 | 179.1 (2) | C24—C25—C26—C27 | −0.8 (4) |
C4—C5—C6—C7 | 1.9 (4) | C25—C26—C27—C28 | −0.3 (4) |
C4—C5—C6—C19 | −176.5 (2) | C26—C27—C28—C29 | 0.5 (4) |
C5—C6—C7—C8 | 1.7 (3) | C27—C28—C29—C24 | 0.6 (4) |
C19—C6—C7—C8 | −180.0 (2) | C25—C24—C29—C28 | −1.7 (4) |
C6—C7—C8—C1 | 179.2 (2) | C20—C24—C29—C28 | 179.5 (2) |
C6—C7—C8—C9 | −4.6 (3) | C22—C23—C30—C31 | 167.0 (2) |
C6—C7—C8—Ti | −96.4 (2) | Ti—C23—C30—C31 | −91.9 (3) |
C2—C1—C8—C7 | 178.1 (2) | C22—C23—C30—C35 | −11.9 (4) |
Si—C1—C8—C7 | 30.2 (3) | Ti—C23—C30—C35 | 89.3 (3) |
Ti—C1—C8—C7 | 107.7 (2) | C35—C30—C31—C32 | 1.9 (4) |
C2—C1—C8—C9 | 1.7 (2) | C23—C30—C31—C32 | −177.0 (2) |
Si—C1—C8—C9 | −146.21 (16) | C30—C31—C32—C33 | −1.3 (4) |
Ti—C1—C8—C9 | −68.74 (15) | C31—C32—C33—C34 | −0.2 (4) |
C2—C1—C8—Ti | 70.42 (14) | C32—C33—C34—C35 | 1.0 (4) |
Si—C1—C8—Ti | −77.47 (14) | C33—C34—C35—C30 | −0.3 (4) |
N1—Ti—C8—C7 | −70.93 (18) | C31—C30—C35—C34 | −1.1 (3) |
C20—Ti—C8—C7 | 154.2 (2) | C23—C30—C35—C34 | 177.8 (2) |
Experimental details
Crystal data | |
Chemical formula | [Ti(C19H27NSi)(C16H14)] |
Mr | 551.68 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 11.0726 (6), 20.509 (1), 13.9311 (8) |
β (°) | 112.020 (1) |
V (Å3) | 2932.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.19 × 0.15 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART diffractometer |
Absorption correction | Analytical integration, based on measured indexed faces (SHELXTL; Sheldrick, 1998) |
Tmin, Tmax | 0.931, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20107, 6740, 4070 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.103, 0.96 |
No. of reflections | 6740 |
No. of parameters | 383 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.31 |
Computer programs: SMART (Bruker, 1998), SMART and SAINT (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXTL.
Ti—N1 | 1.963 (2) | Ti—C9 | 2.490 (2) |
Ti—C20 | 2.217 (2) | C20—C21 | 1.416 (3) |
Ti—C23 | 2.233 (2) | C20—H20 | 0.93 (2) |
Ti—C1 | 2.242 (2) | C21—C22 | 1.397 (3) |
Ti—C21 | 2.295 (2) | C21—H21 | 0.96 (2) |
Ti—C22 | 2.295 (2) | C22—C23 | 1.419 (3) |
Ti—C8 | 2.334 (2) | C22—H22 | 0.98 (2) |
Ti—C2 | 2.355 (2) | C23—H23 | 0.99 (2) |
Ti—C3 | 2.476 (2) | ||
Cp—Ti—N1 | 110.40 (8) | C20—Ti—C23 | 86.82 (8) |
N1—Ti—C20 | 99.09 (8) | C22—C21—C20 | 125.7 (2) |
N1—Ti—C23 | 99.33 (8) | C21—C22—C23 | 126.1 (2) |
C12—C13—C14—C15 | −20.5 (2) | C20—C21—C22—C23 | −0.6 (4) |
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Constrained-geometry catalysts are a very important catalyst family which has had a major impact on homogeneous olefin polymerization technologies (Stevens et al., 1991; McKnight & Waymouth, 1998). In this catalyst family, constrained-geometry titanium(II)–diene complexes, in particular, offer structural diversity and unique olefin polymerization activity (Devore et al., 1995). A common procedure used for the preparation of a variety of constrained-geometry titanium–diene complexes is to react the corresponding dichloride precursor with two equivalents of nBuLi in the presence of excess diene. In the course of structure–activity studies of the constrained-geometry catalysts having ancilliary (η5:η1-C5Me4SiMe2NtBu), we found that when replacing tBu of the tBuN group in the ligand with less bulky secondary C atoms, such as cyclobutyl, the diene complex cannot be obtained with the common procedure. Considering the reactivity of the α-H atom of the N-cyclobutyl group, we found that the use of the milder nBuMgBr reagent instead of nBuLi successfully offered a desired titanium(II)–diene complex, viz. Me2Si(η5-2,3,4,6-Me4C9H2)(C4H7N)Ti(s-cis-η4-1, 4-Ph2C4H4), (I), the structure of which is reported here.
The molecular structure of the title compound is depicted in Fig. 1 and selected geometric parameters are given in Table 1. The Ti metal center is coordinated in a distorted tetrahedral geometry by an η5-indenyl ligand, a dimethylsilyl-bridged N-cyclobutylamido ligand and a 1,4-diphenyl-1,3-butadiene ligand in a `prone' π-fashion (Dahlmann et al., 2000; Devore et al., 1995; Erker et al., 1985; Yasuda et al., 1985). A Cp—Ti—N angle (Cp is the centroid of the indenyl five-membered ring) of 110.40 (8)° reflects the openness of the coordination sphere about Ti.
The 1,4-diphenyl-1,3-butadiene ligand adopts an s-cis orientation with the diene being bound to Ti in a π-fashion. The two Ti—C(terminal) diene distances [Ti—C20 = 2.217 (2) Å and Ti—C23 = 2.233 (2) Å] differ from the two Ti—C(internal) diene distances [Ti—C21 = 2.295 (2) Å and Ti—C22 = 2.295 (2) Å] by only 0.070 Å. The very small C—C distance differences [C20—C21 = 1.416 (3) Å, C21—C22 = 1.397 (3) Å and C22—C23 = 1.419 (3) Å] in the diene ligand also support the assignment of a predominantly π-bound diene ligand (Dahlmann et al., 2000; Devore et al., 1995). A C20—C21—C22—C23 torsion angle of -0.6 (4)° reflects the coplanarity of these atoms.
The Ti—N distance of 1.963 (2) Å compares well with those in typical tBuN constrained-geometry TiII complexes (Dahlmann et al., 2000; Devore et al., 1995), but is considerably longer than in typical TiIV amide complexes (Lappert et al., 1980).