Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013089/om6099sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013089/om6099IIsup2.hkl |
CCDC reference: 197476
Sodium naphthalenide was prepared by combining naphthalene (1.63 g, 12.7 mmol) and sodium (0.31 g, 13 mmol) in dry THF (100 ml) under N2 and allowing the dark-green solution to vigorously stir for 1 h. To the vigorously stirred sodium naphthalenide solution at 195 K was added in one portion a solution of 1,3,6-tri-tert-butylfulvene (3.00 g, 12.2 mmol) in dry THF (50 ml) at 195 K. The color of the reaction mixture immediately faded from dark-green to red, and the red solution was allowed to stir for 30 min at 195 K under N2. The reaction mixture was allowed to slowly warm to room temperature, and THF removed under vacuum. Dry CH3CN (50 ml) was added to the resulting crude orange solid under N2, and the mixture exposed to air. Ammonium chloride (3 ml, 5 M, 15 mmol) was added to the CH3CN solution, resulting in the precipitation of a white solid. The white solid was filtered, washed with CH3CN (30 ml), and dissolved in C6H6 (50 ml). Filtration of solids followed by removal of C6H6 and vacuum drying yielded 2.37 g (79%) of the dimer (II) as a white solid. Crystals suitable for single-crystal X-ray analysis were obtained from 50/50 MeOH/C6H6 as colorless and transparent prisms with well defined faces. 1H NMR 200 MHz (C6D6, 303 K, p.p.m.): δ 1.14, 1.15, 1.41 (s, 54H, tBu); 2.96 (broad s, 4H, ring CH2); 3.43 (s, 2 H, bridge CHtBu); 5.86 (m, 2H, ring CH). 13C NMR 75.5 MHz (C6D6, 303 K, p.p.m.): δ 30.8, 31.2, 33.0 [C(CH3)3]; 32.7, 35.7, 36.9 [C(CH3)3]; 40.4 (ring CH2); 45.7 (CHtBu); 131.5 (ring CH); 139.4, 145.2, 148.1 (ring C). Selected FT–IR (KBr pellet, cm−1): 3104 (w, νringCH); 2958, 2903, 2866 (s, νCH); 1620 (m, νC═C). M.p. = 433.1 K decomposition (DSC). The measured density at 173 K was obtained by correcting the measured density at room temperature (0.954, flotation) to 173 K using the room-temperature diffraction data [a = 16.4307 (10) Å, b = 10.5281 (7) Å, c = 19.8552 (12) Å, β = 96.2200 (10)° and V = 3414.4 (4) Å3].
H atoms on C atoms were placed in calculated positions and constrained to ride on the C atom with usual bond lengths. The Ueq values were 1.5 times (methyl groups) the Ueq values of the corresponding C atoms.
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C36H62 | F(000) = 1112 |
Mr = 494.89 | Dx = 0.983 Mg m−3 Dm = 0.974 Mg m−3 Dm measured by correction from room temp data |
Monoclinic, P21/c | Melting point: 160.1 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.279 (1) Å | Cell parameters from 4491 reflections |
b = 10.5194 (8) Å | θ = 2.3–22.6° |
c = 19.680 (2) Å | µ = 0.05 mm−1 |
β = 96.935 (1)° | T = 173 K |
V = 3345.4 (5) Å3 | Prism, colourless |
Z = 4 | 0.45 × 0.27 × 0.13 mm |
Bruker CCD area-detector diffractometer | 7984 independent reflections |
Radiation source: fine-focus sealed tube | 5492 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ϕ and ω scans | θmax = 28.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −20→20 |
Tmin = 0.84, Tmax = 0.99 | k = −13→13 |
28797 measured reflections | l = −25→25 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0727P)2 + 0.6485P] where P = (Fo2 + 2Fc2)/3 |
7984 reflections | (Δ/σ)max = 0.006 |
343 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C36H62 | V = 3345.4 (5) Å3 |
Mr = 494.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.279 (1) Å | µ = 0.05 mm−1 |
b = 10.5194 (8) Å | T = 173 K |
c = 19.680 (2) Å | 0.45 × 0.27 × 0.13 mm |
β = 96.935 (1)° |
Bruker CCD area-detector diffractometer | 7984 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 5492 reflections with I > 2σ(I) |
Tmin = 0.84, Tmax = 0.99 | Rint = 0.047 |
28797 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
7984 reflections | Δρmin = −0.17 e Å−3 |
343 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 | 0.18486 (8) | 0.23571 (13) | 0.07026 (7) | 0.0249 (3) | |
H1 | 0.2078 | 0.1474 | 0.0733 | 0.030* | |
C2 | 0.18017 (9) | 0.27894 (13) | 0.14723 (7) | 0.0259 (3) | |
H2 | 0.1198 | 0.2842 | 0.1520 | 0.031* | |
C3 | 0.21505 (9) | 0.41041 (13) | 0.16677 (7) | 0.0263 (3) | |
C4 | 0.18070 (9) | 0.51107 (14) | 0.19612 (7) | 0.0304 (3) | |
C5 | 0.24743 (10) | 0.61145 (16) | 0.21167 (9) | 0.0391 (4) | |
H5A | 0.2317 | 0.6912 | 0.1867 | 0.047* | |
H5B | 0.2565 | 0.6300 | 0.2613 | 0.047* | |
C6 | 0.32375 (9) | 0.55541 (15) | 0.18804 (8) | 0.0319 (3) | |
C7 | 0.30320 (9) | 0.44127 (14) | 0.16167 (7) | 0.0286 (3) | |
H7 | 0.3403 | 0.3865 | 0.1421 | 0.034* | |
C8 | 0.24254 (8) | 0.31154 (13) | 0.03031 (7) | 0.0237 (3) | |
C9 | 0.22705 (9) | 0.44851 (13) | 0.01616 (7) | 0.0257 (3) | |
H9 | 0.1865 | 0.4976 | 0.0352 | 0.031* | |
C10 | 0.27746 (9) | 0.49392 (14) | −0.02679 (7) | 0.0280 (3) | |
C11 | 0.33397 (9) | 0.38851 (14) | −0.04231 (8) | 0.0314 (3) | |
H11A | 0.3923 | 0.4102 | −0.0264 | 0.038* | |
H11B | 0.3286 | 0.3713 | −0.0921 | 0.038* | |
C12 | 0.30633 (9) | 0.27425 (13) | −0.00365 (7) | 0.0259 (3) | |
C13 | 0.09684 (9) | 0.22455 (14) | 0.02584 (8) | 0.0310 (3) | |
C14 | 0.03887 (11) | 0.13612 (18) | 0.06007 (9) | 0.0452 (4) | |
H14A | 0.0275 | 0.1732 | 0.1037 | 0.068* | |
H14B | 0.0653 | 0.0530 | 0.0685 | 0.068* | |
H14C | −0.0132 | 0.1258 | 0.0299 | 0.068* | |
C15 | 0.05237 (10) | 0.35231 (17) | 0.01247 (9) | 0.0426 (4) | |
H15A | 0.0772 | 0.3989 | −0.0230 | 0.064* | |
H15B | 0.0578 | 0.4025 | 0.0547 | 0.064* | |
H15C | −0.0064 | 0.3372 | −0.0028 | 0.064* | |
C16 | 0.10725 (11) | 0.16505 (17) | −0.04391 (8) | 0.0416 (4) | |
H16A | 0.0530 | 0.1571 | −0.0711 | 0.062* | |
H16B | 0.1325 | 0.0807 | −0.0370 | 0.062* | |
H16C | 0.1430 | 0.2194 | −0.0682 | 0.062* | |
C17 | 0.21699 (10) | 0.17776 (15) | 0.20271 (8) | 0.0350 (4) | |
C18 | 0.17962 (13) | 0.04484 (16) | 0.18782 (9) | 0.0470 (4) | |
H18A | 0.1955 | 0.0133 | 0.1444 | 0.071* | |
H18B | 0.1192 | 0.0499 | 0.1848 | 0.071* | |
H18C | 0.2004 | −0.0134 | 0.2248 | 0.071* | |
C19 | 0.19324 (13) | 0.21774 (19) | 0.27306 (8) | 0.0497 (5) | |
H19A | 0.2176 | 0.1580 | 0.3081 | 0.075* | |
H19B | 0.1329 | 0.2171 | 0.2717 | 0.075* | |
H19C | 0.2142 | 0.3035 | 0.2842 | 0.075* | |
C20 | 0.31136 (11) | 0.16603 (17) | 0.20941 (10) | 0.0476 (4) | |
H20A | 0.3287 | 0.0904 | 0.2364 | 0.071* | |
H20B | 0.3365 | 0.2417 | 0.2323 | 0.071* | |
H20C | 0.3292 | 0.1585 | 0.1638 | 0.071* | |
C21 | 0.09488 (10) | 0.54331 (16) | 0.21564 (8) | 0.0380 (4) | |
C22 | 0.02763 (11) | 0.4425 (2) | 0.20039 (12) | 0.0587 (6) | |
H22A | 0.0197 | 0.4246 | 0.1512 | 0.088* | |
H22B | −0.0243 | 0.4738 | 0.2147 | 0.088* | |
H22C | 0.0444 | 0.3644 | 0.2255 | 0.088* | |
C23 | 0.10156 (14) | 0.5706 (3) | 0.29263 (11) | 0.0766 (8) | |
H23A | 0.0463 | 0.5872 | 0.3056 | 0.115* | |
H23B | 0.1368 | 0.6451 | 0.3034 | 0.115* | |
H23C | 0.1258 | 0.4969 | 0.3181 | 0.115* | |
C24 | 0.06397 (14) | 0.6639 (2) | 0.17677 (15) | 0.0763 (7) | |
H24A | 0.0633 | 0.6500 | 0.1275 | 0.114* | |
H24B | 0.1010 | 0.7350 | 0.1911 | 0.114* | |
H24C | 0.0079 | 0.6839 | 0.1869 | 0.114* | |
C25 | 0.40737 (10) | 0.62100 (17) | 0.19631 (9) | 0.0411 (4) | |
C26 | 0.44144 (13) | 0.6234 (2) | 0.27277 (10) | 0.0688 (7) | |
H26A | 0.4036 | 0.6716 | 0.2982 | 0.103* | |
H26B | 0.4960 | 0.6640 | 0.2784 | 0.103* | |
H26C | 0.4463 | 0.5362 | 0.2903 | 0.103* | |
C27 | 0.39872 (14) | 0.75785 (19) | 0.16986 (13) | 0.0652 (6) | |
H27A | 0.3728 | 0.7576 | 0.1223 | 0.098* | |
H27B | 0.4536 | 0.7971 | 0.1723 | 0.098* | |
H27C | 0.3642 | 0.8065 | 0.1981 | 0.098* | |
C28 | 0.46861 (11) | 0.5494 (2) | 0.15733 (11) | 0.0542 (5) | |
H28A | 0.4766 | 0.4633 | 0.1759 | 0.081* | |
H28B | 0.5217 | 0.5943 | 0.1623 | 0.081* | |
H28C | 0.4468 | 0.5447 | 0.1087 | 0.081* | |
C29 | 0.27782 (10) | 0.62571 (14) | −0.05826 (8) | 0.0355 (4) | |
C30 | 0.21829 (12) | 0.71369 (16) | −0.02706 (11) | 0.0506 (5) | |
H30A | 0.1622 | 0.6784 | −0.0348 | 0.076* | |
H30B | 0.2190 | 0.7977 | −0.0485 | 0.076* | |
H30C | 0.2354 | 0.7217 | 0.0222 | 0.076* | |
C31 | 0.36537 (12) | 0.68141 (17) | −0.04733 (10) | 0.0497 (5) | |
H31A | 0.3834 | 0.6890 | 0.0018 | 0.075* | |
H31B | 0.3653 | 0.7656 | −0.0686 | 0.075* | |
H31C | 0.4033 | 0.6252 | −0.0682 | 0.075* | |
C32 | 0.25126 (16) | 0.61519 (18) | −0.13537 (10) | 0.0614 (6) | |
H32A | 0.2901 | 0.5601 | −0.1559 | 0.092* | |
H32B | 0.2512 | 0.6999 | −0.1561 | 0.092* | |
H32C | 0.1955 | 0.5788 | −0.1434 | 0.092* | |
C33 | 0.35463 (10) | 0.15013 (14) | −0.00848 (8) | 0.0348 (4) | |
C34 | 0.44204 (13) | 0.1711 (2) | 0.02756 (16) | 0.0822 (8) | |
H34A | 0.4391 | 0.1998 | 0.0746 | 0.123* | |
H34B | 0.4701 | 0.2358 | 0.0029 | 0.123* | |
H34C | 0.4731 | 0.0912 | 0.0283 | 0.123* | |
C35 | 0.3584 (2) | 0.1166 (2) | −0.08371 (11) | 0.0839 (9) | |
H35A | 0.3874 | 0.0355 | −0.0866 | 0.126* | |
H35B | 0.3882 | 0.1835 | −0.1053 | 0.126* | |
H35C | 0.3021 | 0.1093 | −0.1074 | 0.126* | |
C36 | 0.32023 (13) | 0.03310 (16) | 0.02391 (11) | 0.0524 (5) | |
H36A | 0.3545 | −0.0409 | 0.0163 | 0.079* | |
H36B | 0.2633 | 0.0179 | 0.0031 | 0.079* | |
H36C | 0.3208 | 0.0470 | 0.0732 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0248 (7) | 0.0218 (7) | 0.0287 (7) | −0.0018 (5) | 0.0057 (6) | −0.0016 (6) |
C2 | 0.0249 (7) | 0.0255 (7) | 0.0282 (7) | −0.0028 (6) | 0.0073 (6) | −0.0024 (6) |
C3 | 0.0252 (7) | 0.0293 (7) | 0.0251 (7) | −0.0029 (6) | 0.0058 (6) | −0.0029 (6) |
C4 | 0.0288 (8) | 0.0327 (8) | 0.0304 (7) | −0.0024 (6) | 0.0073 (6) | −0.0049 (6) |
C5 | 0.0384 (9) | 0.0343 (9) | 0.0456 (9) | −0.0049 (7) | 0.0095 (7) | −0.0146 (7) |
C6 | 0.0307 (8) | 0.0345 (8) | 0.0310 (8) | −0.0060 (6) | 0.0060 (6) | −0.0063 (6) |
C7 | 0.0248 (7) | 0.0318 (8) | 0.0298 (7) | −0.0014 (6) | 0.0061 (6) | −0.0044 (6) |
C8 | 0.0234 (7) | 0.0211 (7) | 0.0265 (7) | −0.0017 (5) | 0.0026 (5) | −0.0032 (5) |
C9 | 0.0265 (7) | 0.0202 (7) | 0.0305 (7) | −0.0002 (5) | 0.0045 (6) | −0.0024 (6) |
C10 | 0.0302 (8) | 0.0230 (7) | 0.0306 (7) | −0.0050 (6) | 0.0029 (6) | −0.0018 (6) |
C11 | 0.0303 (8) | 0.0308 (8) | 0.0348 (8) | −0.0031 (6) | 0.0113 (6) | 0.0005 (6) |
C12 | 0.0249 (7) | 0.0228 (7) | 0.0302 (7) | −0.0025 (5) | 0.0044 (6) | −0.0026 (6) |
C13 | 0.0275 (8) | 0.0330 (8) | 0.0329 (8) | −0.0084 (6) | 0.0054 (6) | −0.0039 (6) |
C14 | 0.0372 (9) | 0.0554 (11) | 0.0434 (10) | −0.0224 (8) | 0.0062 (8) | −0.0057 (8) |
C15 | 0.0256 (8) | 0.0478 (10) | 0.0530 (10) | −0.0004 (7) | −0.0016 (7) | −0.0014 (8) |
C16 | 0.0386 (9) | 0.0501 (10) | 0.0354 (9) | −0.0097 (8) | 0.0017 (7) | −0.0086 (8) |
C17 | 0.0399 (9) | 0.0339 (8) | 0.0313 (8) | −0.0024 (7) | 0.0050 (7) | 0.0024 (7) |
C18 | 0.0646 (12) | 0.0358 (9) | 0.0407 (9) | −0.0100 (8) | 0.0062 (8) | 0.0110 (7) |
C19 | 0.0651 (12) | 0.0541 (11) | 0.0305 (9) | 0.0035 (9) | 0.0078 (8) | 0.0056 (8) |
C20 | 0.0434 (10) | 0.0418 (10) | 0.0557 (11) | 0.0060 (8) | −0.0018 (8) | 0.0103 (8) |
C21 | 0.0314 (8) | 0.0456 (9) | 0.0387 (9) | 0.0035 (7) | 0.0108 (7) | −0.0131 (7) |
C22 | 0.0296 (9) | 0.0722 (14) | 0.0784 (14) | −0.0044 (9) | 0.0235 (9) | −0.0260 (11) |
C23 | 0.0485 (12) | 0.136 (2) | 0.0488 (12) | −0.0065 (13) | 0.0220 (10) | −0.0376 (13) |
C24 | 0.0504 (13) | 0.0710 (15) | 0.110 (2) | 0.0255 (11) | 0.0205 (13) | 0.0147 (14) |
C25 | 0.0363 (9) | 0.0479 (10) | 0.0393 (9) | −0.0187 (8) | 0.0049 (7) | −0.0098 (8) |
C26 | 0.0475 (12) | 0.1079 (19) | 0.0499 (12) | −0.0301 (12) | 0.0016 (9) | −0.0178 (12) |
C27 | 0.0633 (14) | 0.0460 (11) | 0.0886 (16) | −0.0255 (10) | 0.0183 (12) | −0.0064 (11) |
C28 | 0.0337 (10) | 0.0680 (13) | 0.0627 (12) | −0.0158 (9) | 0.0134 (9) | −0.0123 (10) |
C29 | 0.0479 (10) | 0.0221 (7) | 0.0367 (8) | −0.0073 (7) | 0.0051 (7) | 0.0025 (6) |
C30 | 0.0570 (12) | 0.0234 (8) | 0.0727 (13) | 0.0011 (8) | 0.0131 (10) | 0.0077 (8) |
C31 | 0.0564 (11) | 0.0325 (9) | 0.0635 (12) | −0.0164 (8) | 0.0209 (9) | 0.0011 (8) |
C32 | 0.1021 (18) | 0.0372 (10) | 0.0421 (10) | −0.0082 (10) | −0.0026 (11) | 0.0122 (8) |
C33 | 0.0338 (8) | 0.0289 (8) | 0.0436 (9) | 0.0074 (6) | 0.0121 (7) | −0.0030 (7) |
C34 | 0.0388 (11) | 0.0489 (12) | 0.154 (3) | 0.0143 (9) | −0.0098 (13) | −0.0035 (14) |
C35 | 0.148 (2) | 0.0548 (13) | 0.0561 (13) | 0.0503 (15) | 0.0436 (15) | −0.0002 (10) |
C36 | 0.0627 (12) | 0.0248 (8) | 0.0731 (13) | 0.0131 (8) | 0.0216 (10) | −0.0017 (8) |
C1—C8 | 1.521 (2) | C20—H20C | 0.9800 |
C1—C13 | 1.590 (2) | C21—C22 | 1.528 (2) |
C1—C2 | 1.592 (2) | C21—C23 | 1.533 (3) |
C1—H1 | 1.0000 | C21—C24 | 1.535 (3) |
C2—C3 | 1.526 (2) | C22—H22A | 0.9800 |
C2—C17 | 1.589 (2) | C22—H22B | 0.9800 |
C2—H2 | 1.0000 | C22—H22C | 0.9800 |
C3—C4 | 1.359 (2) | C23—H23A | 0.9800 |
C3—C7 | 1.487 (2) | C23—H23B | 0.9800 |
C4—C5 | 1.519 (2) | C23—H23C | 0.9800 |
C4—C21 | 1.531 (2) | C24—H24A | 0.9800 |
C5—C6 | 1.499 (2) | C24—H24B | 0.9800 |
C5—H5A | 0.9900 | C24—H24C | 0.9800 |
C5—H5B | 0.9900 | C25—C28 | 1.528 (3) |
C6—C7 | 1.335 (2) | C25—C27 | 1.532 (3) |
C6—C25 | 1.517 (2) | C25—C26 | 1.540 (3) |
C7—H7 | 0.9500 | C26—H26A | 0.9800 |
C8—C12 | 1.359 (2) | C26—H26B | 0.9800 |
C8—C9 | 1.483 (2) | C26—H26C | 0.9800 |
C9—C10 | 1.335 (2) | C27—H27A | 0.9800 |
C9—H9 | 0.9500 | C27—H27B | 0.9800 |
C10—C11 | 1.496 (2) | C27—H27C | 0.9800 |
C10—C29 | 1.519 (2) | C28—H28A | 0.9800 |
C11—C12 | 1.519 (2) | C28—H28B | 0.9800 |
C11—H11A | 0.9900 | C28—H28C | 0.9800 |
C11—H11B | 0.9900 | C29—C30 | 1.522 (2) |
C12—C33 | 1.533 (2) | C29—C32 | 1.531 (2) |
C13—C15 | 1.534 (2) | C29—C31 | 1.532 (2) |
C13—C16 | 1.537 (2) | C30—H30A | 0.9800 |
C13—C14 | 1.537 (2) | C30—H30B | 0.9800 |
C14—H14A | 0.9800 | C30—H30C | 0.9800 |
C14—H14B | 0.9800 | C31—H31A | 0.9800 |
C14—H14C | 0.9800 | C31—H31B | 0.9800 |
C15—H15A | 0.9800 | C31—H31C | 0.9800 |
C15—H15B | 0.9800 | C32—H32A | 0.9800 |
C15—H15C | 0.9800 | C32—H32B | 0.9800 |
C16—H16A | 0.9800 | C32—H32C | 0.9800 |
C16—H16B | 0.9800 | C33—C36 | 1.524 (2) |
C16—H16C | 0.9800 | C33—C34 | 1.527 (3) |
C17—C20 | 1.531 (2) | C33—C35 | 1.530 (3) |
C17—C18 | 1.539 (2) | C34—H34A | 0.9800 |
C17—C19 | 1.540 (2) | C34—H34B | 0.9800 |
C18—H18A | 0.9800 | C34—H34C | 0.9800 |
C18—H18B | 0.9800 | C35—H35A | 0.9800 |
C18—H18C | 0.9800 | C35—H35B | 0.9800 |
C19—H19A | 0.9800 | C35—H35C | 0.9800 |
C19—H19B | 0.9800 | C36—H36A | 0.9800 |
C19—H19C | 0.9800 | C36—H36B | 0.9800 |
C20—H20A | 0.9800 | C36—H36C | 0.9800 |
C20—H20B | 0.9800 | ||
C8—C1—C13 | 109.03 (11) | C22—C21—C4 | 116.80 (13) |
C8—C1—C2 | 116.44 (11) | C22—C21—C23 | 106.73 (16) |
C13—C1—C2 | 113.61 (11) | C4—C21—C23 | 109.36 (14) |
C8—C1—H1 | 105.6 | C22—C21—C24 | 106.98 (17) |
C13—C1—H1 | 105.6 | C4—C21—C24 | 108.19 (15) |
C2—C1—H1 | 105.6 | C23—C21—C24 | 108.52 (18) |
C3—C2—C17 | 109.62 (12) | C21—C22—H22A | 109.5 |
C3—C2—C1 | 116.06 (11) | C21—C22—H22B | 109.5 |
C17—C2—C1 | 113.88 (11) | H22A—C22—H22B | 109.5 |
C3—C2—H2 | 105.4 | C21—C22—H22C | 109.5 |
C17—C2—H2 | 105.4 | H22A—C22—H22C | 109.5 |
C1—C2—H2 | 105.4 | H22B—C22—H22C | 109.5 |
C4—C3—C7 | 107.99 (12) | C21—C23—H23A | 109.5 |
C4—C3—C2 | 130.81 (13) | C21—C23—H23B | 109.5 |
C7—C3—C2 | 120.91 (12) | H23A—C23—H23B | 109.5 |
C3—C4—C5 | 107.84 (13) | C21—C23—H23C | 109.5 |
C3—C4—C21 | 135.58 (14) | H23A—C23—H23C | 109.5 |
C5—C4—C21 | 116.58 (13) | H23B—C23—H23C | 109.5 |
C6—C5—C4 | 105.27 (12) | C21—C24—H24A | 109.5 |
C6—C5—H5A | 110.7 | C21—C24—H24B | 109.5 |
C4—C5—H5A | 110.7 | H24A—C24—H24B | 109.5 |
C6—C5—H5B | 110.7 | C21—C24—H24C | 109.5 |
C4—C5—H5B | 110.7 | H24A—C24—H24C | 109.5 |
H5A—C5—H5B | 108.8 | H24B—C24—H24C | 109.5 |
C7—C6—C5 | 107.24 (13) | C6—C25—C28 | 110.70 (13) |
C7—C6—C25 | 129.07 (15) | C6—C25—C27 | 110.27 (15) |
C5—C6—C25 | 123.67 (13) | C28—C25—C27 | 109.36 (16) |
C6—C7—C3 | 111.65 (13) | C6—C25—C26 | 108.97 (14) |
C6—C7—H7 | 124.2 | C28—C25—C26 | 108.60 (16) |
C3—C7—H7 | 124.2 | C27—C25—C26 | 108.91 (16) |
C12—C8—C9 | 108.10 (12) | C25—C26—H26A | 109.5 |
C12—C8—C1 | 131.21 (12) | C25—C26—H26B | 109.5 |
C9—C8—C1 | 120.32 (12) | H26A—C26—H26B | 109.5 |
C10—C9—C8 | 111.27 (12) | C25—C26—H26C | 109.5 |
C10—C9—H9 | 124.4 | H26A—C26—H26C | 109.5 |
C8—C9—H9 | 124.4 | H26B—C26—H26C | 109.5 |
C9—C10—C11 | 107.71 (12) | C25—C27—H27A | 109.5 |
C9—C10—C29 | 128.14 (14) | C25—C27—H27B | 109.5 |
C11—C10—C29 | 124.10 (13) | H27A—C27—H27B | 109.5 |
C10—C11—C12 | 104.92 (11) | C25—C27—H27C | 109.5 |
C10—C11—H11A | 110.8 | H27A—C27—H27C | 109.5 |
C12—C11—H11A | 110.8 | H27B—C27—H27C | 109.5 |
C10—C11—H11B | 110.8 | C25—C28—H28A | 109.5 |
C12—C11—H11B | 110.8 | C25—C28—H28B | 109.5 |
H11A—C11—H11B | 108.8 | H28A—C28—H28B | 109.5 |
C8—C12—C11 | 107.94 (12) | C25—C28—H28C | 109.5 |
C8—C12—C33 | 134.79 (13) | H28A—C28—H28C | 109.5 |
C11—C12—C33 | 117.23 (12) | H28B—C28—H28C | 109.5 |
C15—C13—C16 | 107.72 (14) | C10—C29—C30 | 110.88 (13) |
C15—C13—C14 | 107.66 (13) | C10—C29—C32 | 108.89 (13) |
C16—C13—C14 | 106.54 (13) | C30—C29—C32 | 109.06 (16) |
C15—C13—C1 | 113.89 (12) | C10—C29—C31 | 109.95 (14) |
C16—C13—C1 | 109.38 (12) | C30—C29—C31 | 109.73 (14) |
C14—C13—C1 | 111.34 (13) | C32—C29—C31 | 108.27 (15) |
C13—C14—H14A | 109.5 | C29—C30—H30A | 109.5 |
C13—C14—H14B | 109.5 | C29—C30—H30B | 109.5 |
H14A—C14—H14B | 109.5 | H30A—C30—H30B | 109.5 |
C13—C14—H14C | 109.5 | C29—C30—H30C | 109.5 |
H14A—C14—H14C | 109.5 | H30A—C30—H30C | 109.5 |
H14B—C14—H14C | 109.5 | H30B—C30—H30C | 109.5 |
C13—C15—H15A | 109.5 | C29—C31—H31A | 109.5 |
C13—C15—H15B | 109.5 | C29—C31—H31B | 109.5 |
H15A—C15—H15B | 109.5 | H31A—C31—H31B | 109.5 |
C13—C15—H15C | 109.5 | C29—C31—H31C | 109.5 |
H15A—C15—H15C | 109.5 | H31A—C31—H31C | 109.5 |
H15B—C15—H15C | 109.5 | H31B—C31—H31C | 109.5 |
C13—C16—H16A | 109.5 | C29—C32—H32A | 109.5 |
C13—C16—H16B | 109.5 | C29—C32—H32B | 109.5 |
H16A—C16—H16B | 109.5 | H32A—C32—H32B | 109.5 |
C13—C16—H16C | 109.5 | C29—C32—H32C | 109.5 |
H16A—C16—H16C | 109.5 | H32A—C32—H32C | 109.5 |
H16B—C16—H16C | 109.5 | H32B—C32—H32C | 109.5 |
C20—C17—C18 | 108.22 (14) | C36—C33—C34 | 106.93 (16) |
C20—C17—C19 | 107.62 (14) | C36—C33—C35 | 106.15 (16) |
C18—C17—C19 | 106.43 (14) | C34—C33—C35 | 109.76 (19) |
C20—C17—C2 | 113.86 (13) | C36—C33—C12 | 116.43 (13) |
C18—C17—C2 | 111.73 (13) | C34—C33—C12 | 107.72 (14) |
C19—C17—C2 | 108.65 (13) | C35—C33—C12 | 109.72 (14) |
C17—C18—H18A | 109.5 | C33—C34—H34A | 109.5 |
C17—C18—H18B | 109.5 | C33—C34—H34B | 109.5 |
H18A—C18—H18B | 109.5 | H34A—C34—H34B | 109.5 |
C17—C18—H18C | 109.5 | C33—C34—H34C | 109.5 |
H18A—C18—H18C | 109.5 | H34A—C34—H34C | 109.5 |
H18B—C18—H18C | 109.5 | H34B—C34—H34C | 109.5 |
C17—C19—H19A | 109.5 | C33—C35—H35A | 109.5 |
C17—C19—H19B | 109.5 | C33—C35—H35B | 109.5 |
H19A—C19—H19B | 109.5 | H35A—C35—H35B | 109.5 |
C17—C19—H19C | 109.5 | C33—C35—H35C | 109.5 |
H19A—C19—H19C | 109.5 | H35A—C35—H35C | 109.5 |
H19B—C19—H19C | 109.5 | H35B—C35—H35C | 109.5 |
C17—C20—H20A | 109.5 | C33—C36—H36A | 109.5 |
C17—C20—H20B | 109.5 | C33—C36—H36B | 109.5 |
H20A—C20—H20B | 109.5 | H36A—C36—H36B | 109.5 |
C17—C20—H20C | 109.5 | C33—C36—H36C | 109.5 |
H20A—C20—H20C | 109.5 | H36A—C36—H36C | 109.5 |
H20B—C20—H20C | 109.5 | H36B—C36—H36C | 109.5 |
C8—C1—C2—C3 | 15.63 (17) | C8—C1—C13—C15 | −64.50 (15) |
C13—C1—C2—C3 | −112.31 (13) | C2—C1—C13—C15 | 67.17 (16) |
C8—C1—C2—C17 | −113.07 (14) | C8—C1—C13—C16 | 56.07 (15) |
C13—C1—C2—C17 | 118.99 (13) | C2—C1—C13—C16 | −172.26 (12) |
C17—C2—C3—C4 | −102.22 (18) | C8—C1—C13—C14 | 173.55 (12) |
C1—C2—C3—C4 | 127.04 (16) | C2—C1—C13—C14 | −54.78 (16) |
C17—C2—C3—C7 | 70.72 (16) | C3—C2—C17—C20 | −60.56 (17) |
C1—C2—C3—C7 | −60.03 (17) | C1—C2—C17—C20 | 71.34 (16) |
C7—C3—C4—C5 | −0.48 (17) | C3—C2—C17—C18 | 176.47 (13) |
C2—C3—C4—C5 | 173.15 (14) | C1—C2—C17—C18 | −51.63 (17) |
C7—C3—C4—C21 | 179.47 (17) | C3—C2—C17—C19 | 59.34 (16) |
C2—C3—C4—C21 | −6.9 (3) | C1—C2—C17—C19 | −168.76 (13) |
C3—C4—C5—C6 | −0.33 (18) | C3—C4—C21—C22 | 0.3 (3) |
C21—C4—C5—C6 | 179.70 (13) | C5—C4—C21—C22 | −179.76 (16) |
C4—C5—C6—C7 | 1.10 (18) | C3—C4—C21—C23 | 121.6 (2) |
C4—C5—C6—C25 | −177.34 (14) | C5—C4—C21—C23 | −58.5 (2) |
C5—C6—C7—C3 | −1.45 (18) | C3—C4—C21—C24 | −120.4 (2) |
C25—C6—C7—C3 | 176.88 (15) | C5—C4—C21—C24 | 59.5 (2) |
C4—C3—C7—C6 | 1.27 (18) | C7—C6—C25—C28 | 10.8 (2) |
C2—C3—C7—C6 | −173.11 (13) | C5—C6—C25—C28 | −171.13 (16) |
C13—C1—C8—C12 | −105.07 (17) | C7—C6—C25—C27 | 131.94 (19) |
C2—C1—C8—C12 | 124.79 (16) | C5—C6—C25—C27 | −50.0 (2) |
C13—C1—C8—C9 | 67.09 (15) | C7—C6—C25—C26 | −108.6 (2) |
C2—C1—C8—C9 | −63.06 (17) | C5—C6—C25—C26 | 69.5 (2) |
C12—C8—C9—C10 | 1.96 (17) | C9—C10—C29—C30 | 7.9 (2) |
C1—C8—C9—C10 | −171.84 (12) | C11—C10—C29—C30 | −174.96 (15) |
C8—C9—C10—C11 | −2.38 (16) | C9—C10—C29—C32 | −112.10 (19) |
C8—C9—C10—C29 | 175.14 (13) | C11—C10—C29—C32 | 65.0 (2) |
C9—C10—C11—C12 | 1.91 (16) | C9—C10—C29—C31 | 129.43 (17) |
C29—C10—C11—C12 | −175.73 (13) | C11—C10—C29—C31 | −53.43 (19) |
C9—C8—C12—C11 | −0.62 (16) | C8—C12—C33—C36 | 9.2 (3) |
C1—C8—C12—C11 | 172.26 (14) | C11—C12—C33—C36 | −173.40 (15) |
C9—C8—C12—C33 | 176.93 (15) | C8—C12—C33—C34 | −110.8 (2) |
C1—C8—C12—C33 | −10.2 (3) | C11—C12—C33—C34 | 66.6 (2) |
C10—C11—C12—C8 | −0.72 (16) | C8—C12—C33—C35 | 129.8 (2) |
C10—C11—C12—C33 | −178.77 (12) | C11—C12—C33—C35 | −52.9 (2) |
Experimental details
Crystal data | |
Chemical formula | C36H62 |
Mr | 494.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 16.279 (1), 10.5194 (8), 19.680 (2) |
β (°) | 96.935 (1) |
V (Å3) | 3345.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.05 |
Crystal size (mm) | 0.45 × 0.27 × 0.13 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.84, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28797, 7984, 5492 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.158, 1.03 |
No. of reflections | 7984 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.17 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT-Plus (Bruker, 2001), SHELXTL (Bruker, 2001), SHELXTL.
C1—C8 | 1.521 (2) | C13—C15 | 1.534 (2) |
C1—C13 | 1.590 (2) | C13—C16 | 1.537 (2) |
C1—C2 | 1.592 (2) | C13—C14 | 1.537 (2) |
C2—C3 | 1.526 (2) | C17—C20 | 1.531 (2) |
C2—C17 | 1.589 (2) | C17—C18 | 1.539 (2) |
C3—C4 | 1.359 (2) | C17—C19 | 1.540 (2) |
C3—C7 | 1.487 (2) | C21—C22 | 1.528 (2) |
C4—C5 | 1.519 (2) | C21—C23 | 1.533 (3) |
C4—C21 | 1.531 (2) | C21—C24 | 1.535 (3) |
C5—C6 | 1.499 (2) | C25—C28 | 1.528 (3) |
C6—C7 | 1.335 (2) | C25—C27 | 1.532 (3) |
C6—C25 | 1.517 (2) | C25—C26 | 1.540 (3) |
C8—C12 | 1.359 (2) | C29—C30 | 1.522 (2) |
C8—C9 | 1.483 (2) | C29—C32 | 1.531 (2) |
C9—C10 | 1.335 (2) | C29—C31 | 1.532 (2) |
C10—C11 | 1.496 (2) | C33—C36 | 1.524 (2) |
C10—C29 | 1.519 (2) | C33—C34 | 1.527 (3) |
C11—C12 | 1.519 (2) | C33—C35 | 1.530 (3) |
C12—C33 | 1.533 (2) | ||
C8—C1—C13 | 109.03 (11) | C16—C13—C1 | 109.38 (12) |
C8—C1—C2 | 116.44 (11) | C14—C13—C1 | 111.34 (13) |
C13—C1—C2 | 113.61 (11) | C20—C17—C18 | 108.22 (14) |
C3—C2—C17 | 109.62 (12) | C20—C17—C19 | 107.62 (14) |
C3—C2—C1 | 116.06 (11) | C18—C17—C19 | 106.43 (14) |
C17—C2—C1 | 113.88 (11) | C20—C17—C2 | 113.86 (13) |
C4—C3—C7 | 107.99 (12) | C18—C17—C2 | 111.73 (13) |
C4—C3—C2 | 130.81 (13) | C19—C17—C2 | 108.65 (13) |
C7—C3—C2 | 120.91 (12) | C22—C21—C4 | 116.80 (13) |
C3—C4—C5 | 107.84 (13) | C22—C21—C23 | 106.73 (16) |
C3—C4—C21 | 135.58 (14) | C4—C21—C23 | 109.36 (14) |
C5—C4—C21 | 116.58 (13) | C22—C21—C24 | 106.98 (17) |
C6—C5—C4 | 105.27 (12) | C4—C21—C24 | 108.19 (15) |
C7—C6—C5 | 107.24 (13) | C23—C21—C24 | 108.52 (18) |
C7—C6—C25 | 129.07 (15) | C6—C25—C28 | 110.70 (13) |
C5—C6—C25 | 123.67 (13) | C6—C25—C27 | 110.27 (15) |
C6—C7—C3 | 111.65 (13) | C28—C25—C27 | 109.36 (16) |
C12—C8—C9 | 108.10 (12) | C6—C25—C26 | 108.97 (14) |
C12—C8—C1 | 131.21 (12) | C28—C25—C26 | 108.60 (16) |
C9—C8—C1 | 120.32 (12) | C27—C25—C26 | 108.91 (16) |
C10—C9—C8 | 111.27 (12) | C10—C29—C30 | 110.88 (13) |
C9—C10—C11 | 107.71 (12) | C10—C29—C32 | 108.89 (13) |
C9—C10—C29 | 128.14 (14) | C30—C29—C32 | 109.06 (16) |
C11—C10—C29 | 124.10 (13) | C10—C29—C31 | 109.95 (14) |
C10—C11—C12 | 104.92 (11) | C30—C29—C31 | 109.73 (14) |
C8—C12—C11 | 107.94 (12) | C32—C29—C31 | 108.27 (15) |
C8—C12—C33 | 134.79 (13) | C36—C33—C34 | 106.93 (16) |
C11—C12—C33 | 117.23 (12) | C36—C33—C35 | 106.15 (16) |
C15—C13—C16 | 107.72 (14) | C34—C33—C35 | 109.76 (19) |
C15—C13—C14 | 107.66 (13) | C36—C33—C12 | 116.43 (13) |
C16—C13—C14 | 106.54 (13) | C34—C33—C12 | 107.72 (14) |
C15—C13—C1 | 113.89 (12) | C35—C33—C12 | 109.72 (14) |
C8—C1—C2—C3 | 15.63 (17) | C1—C2—C3—C4 | 127.04 (16) |
C13—C1—C2—C17 | 118.99 (13) | C2—C1—C8—C12 | 124.79 (16) |
The reductive dimerization of fulvenes to form bridged-cyclopentadienyl ligands is a versatile synthetic route to ansa-metallocene complexes, which are important in catalytic processes (Long, 1998; Brintzinger et al., 1995; Gomez & Waymouth, 2002; Aitola et al., 2002; Miller & Bercaw, 2002; Angermund et al., 2000; Bogaert et al., 2001; Ihara et al., 2001; Shaltout & Corey, 1995). Methods most commonly used directly incorporate the metal into the ligand framework, and include reaction of fulvenes with activated Ca or Sr (Rieckhoff et al., 1993; Sinnema et al., 2002), Mg/CCl4/TiCl3·3THF or Na(Hg)/TiCl3·3THF (Schwemlein & Brintzinger, 1983), activated lanthanide metals (Recknagel & Edelmann, 1991; Fedushkin et al., 2001), group IV divalent halides (Eisch et al., 1998, 1999) and metal vapors at low temperature (Tacke, Dunne et al., 2001). Fulvene radical anions are key intermediates leading to dimerization in these reactions, and have been studied by theoretical and experimental methods (Tacke, Fox et al., 2001).
Reduction of fulvenes with aromatic hydrocarbon radical anions has also been carried out. Reaction of 6,6-dimethylfulvene with sodium naphthalenide gave a dimer product coupled at the C-1 position on the ring (Oku et al., 1979), while reaction of 6,6-dimethylfulvene with sodium anthracenide followed by TiCl3·3THF was reported to give exclusive formation of the bridged tetramethylethylene-titanocene dichloride (Schwemlein & Brintzinger, 1983). In the reductive coupling of substituted 6-dimethylaminofulvenes with lithium naphthalenide, deamination of proposed bis(cyclopentadienyl) intermediates led to the formation of substituted 6,6'-bifulvenyl compounds (Kawese et al., 1989).
One of our research goals is to investigate the selectivity in reactions of aromatic hydrocarbon radical anions with various substituted fulvenes with an emphasis on obtaining new bis(cyclopentadienyl) compounds useful as ligands for the formation of ansa-metallocene complexes. Recently, we carried out the aromatic hydrocarbon radical anion dimerization of the sterically demanding 1,3,6-tri(tert-butyl)fulvene, (I) (Johnson et al., 1997). A unique feature of this chemistry is the almost exclusive formation of the racemic dimer (II) (79%), from the reaction of (I) and sodium naphthalenide. The dimer (II) is formed by protonation of the isolable bis(cyclopentadienylethane) intermediate. To our knowledge, the dimer (II) is the first reported case of a C2 ansa-cyclopentadiene ligand synthesized by fulvene dimerization using aromatic hydrocarbon radical anions. Research in our laboratory on the utility of (II) for the synthesis of ansa-metallocenes is in progress.
Single-crystal X-ray diffraction results for (II) show a nearly C2 symmetric structure adopted as a result of selective coupling of two 1,3,6-tri-tert-butylfulvene units (Fig. 1 and Table 1). The cyclopentadiene rings are nearly eclipsed in (II) (Fig. 2), with a torsion angle of 119.0 (1)° between the tert-butyl groups of the ansa bridge. C—C bond distances in (II) are comparable to those in a recently reported crystal structure of the related ansa-cyclopentadiene ligand C5H5CMe2CMe2C5H5 (Tacke, Dunne et al., 2001). The C1—C2 bond distance in (II) [1.592 (2) Å] is slightly shorter than in C5H5CMe2CMe2C5H5 [1.600 (3) Å], but consistent with an elongated bridge bond from steric interaction of bulky tert-butyl groups.