184
Organometallics 1990, 9, 184-189
tolysis. Within experimental error, the relative amounts of the three isomers remained constant. Acknowledgment. We gratefully acknowledge support for this work in part by the National Science Foundation and in part by the donors of the Petroleum Research Fund, administered by the American Chemical Society. We also acknowledge with appreciation the assistance of Otto Phanstiel in the early stages of the fluorocyclopropane work. D.J.C. gratefully acknowledges support from the UF Division of Sponsored Research. Registry No. 6c, 114944-66-0;6d, 114944-67-1;6e,123724-41-4; 6f, 123724-44-7; trans-6g, 123724-50-5; cis-6g, 123807-09-0; trans-6h, 123724-45-8;cis-6h, 123807-06-7;8c, 114944-68-2;9c,
114944-69-3; 9d, 114944-70-6; exo-lOc, 114944-72-8; 10e, 123724-43-6;exopyn-log, 35429-53-9;exo,anti-log, 35429-52-8; exo,anti-lOh, 123724-46-9; endo,syn-lOh, 123807-07-8; endo,anti-lOh, 123807-08-9; exo,syn-lOh, 123807-11-4; exo,syn-llc, 114944-71-7; 12, 123724-42-5; trans-13, 123724-51-6; cis-13, 123807-10-3; KFp, 60039-75-0; [CpFe(CO),($-CH,= CHCH,F)]BF,, 123724-49-2; dicarbonyl(~~~-cyclopentadienyl)(V'-cis-1-fluoropropenyl)iron, 123724-47-0; 1bromo-1-ethoxycyclopropane, 95631-62-2; 1-iodo-1-(phenylthio)cyclopropane, 123724-40-3; trans-1-bromo-2-fluorocyclopropane, 116577-38-9; trans-2-methylcyclopropyl bromide, 6142-48-9; epifluorohydrin, 503-09-3; cis-2-methylcyclopropyl bromide, 6142-60-5;2-methylcyclopropanecarboxylicacid chloride, 60733-34-8; 2-methylcyclopropanecarboxylic acid, 29555-02-0; oxalyl chloride, 79-37-8.
Solid-state Structure and Fluxional Solution Behavior of the C0)c Ambident Organometallic Nucleophiles (q3-C7H7)M( (M = Ru, Os) Stephen T. Astley and Josef Takats" Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2
John C. Huffman and William E. Streib Molecular Structure Center, Indiana Universiw, Bloomington, Indiana 47405 Received May 23, 1989
The cycloheptatrienyl carbonyl anions (C7H7)M(C0) 0.0 3928 no. of F > 3.0u(F) 3905 3686 R for averaging 0.018 0.030 0.0268 0.0567 R(F) 0.0575 0.0278 RdF) 1.060 goodness of fit for the 1.645 last cycle 0.52 max A / u for the last 0.35 cycle 0
T a b d 11. Fractional Coordinates" and Equivalent Isotropic Thermal Parameters for (C7H7)Ru(CO)f in l b atom X Y z Bigotb A2 Ru 638.4 (4) 2710.7 (5) 7794 (1) 16 c1 343 (6) 1898 (7) 6466 (7) 23 c2 -369 (6) 2858 (6) 6283 (7) 20 6657 (7) 24 -1573 (6) 2747 (7) C3 1841 (7) 7469 (8) 24 C4 -2244 (6) C5 -1919 (6) 749 (7) 8261 (8) 28 C6 -885 (6) 396 (6) 8389 (8) 25 957 (6) 7640 ( 7 ) 22 C7 169 (6) C8 1869 (6) 2123 (6) 8582 (7) 24 4249 (7) 6920 (7) 26 c9 1306 (6) C10 -529 (6) 2803 (6) 9121 (7) 20 1826 (5) 9032 (5) 33 01 2649 (4) 5158 (5) 6409 (7) 48 02 1738 (5) 03 -1260 (4) 2852 (5) 9854 (5) 30
"Fractional coordinates are XlO'. Big, values are X10. Isotropic values for those atoms refined anisotropically are calculated by using the formula given by; Hamilton, W. C. Acta Crystallogr. 1959, 12, 609. residuals of less then 2 e/A3. All other residual peaks were less than 0.5 e/A3. A summary of t h e crystallographic d a t a for compounds 1b and is presented in Table I. positional and equivalent isotropic parameters of the anion (C~H~)M(CO)C are given in Tables I1 a n d 111. Additional information is available as supplementary material.
Results Solid-state Structure of (C7H7)M(C0)3-Compounds. In the solid state, complexes l b and IC were
Astley et al. Table 111. Fractional Coordinatesn and Equivalent Isotropic Thermal Parameters for (C7H7)Os(CO)f in IC atom X Y z Bi_,bAZ os 653.6 (2) 2716.0 (2) 7788.8 (2) 13 c1 346 (4) 1878 (5) 6478 (5) 20 c2 2840 (5) 6297 (5) 19 -384 (4) C3 -1580 (5) 2736 (5) 6665 (6) 21 C4 -2247 (5) 1828 (5) 7473 (5) 23 C5 -1924 (5) 730 (5) 8275 (6) 25 389 (5) 8388 (6) 24 C6 -897 (5) c7 1310 (5) 4254 (5) 6925 (6) 25 C8 1886 (4) 2146 (5) 8578 (5) 21 c9 1310 (5) 4254 (5) 6925 (6) 25 C10 -502 (4) 2809 (5) 9104 (5) 19 01 2655 (3) 1843 (4) 9036 (4) 30 5180 (4) 6390 (5) 43 02 1726 (4) 03 -1224 (3) 2868 (4) 9851 (4) 27
"Fractional coordinates are N O 4 . Bise values are X10. Isotropic values for those atoms refined anisotropically are calculated by using the formula given by; Hamilton, W. C. Acta Crystallogr. 1959, 12, 609. Table IV. Selected Bond Lengths and Angles for Anions 1, (v~-C~H~)M(C (M O )=~Fe, Ru, Os) Fe" ( l a ) Ru (lb) Os (IC) Bond Length 1.26 1.16 1.25 metal radiusb M-C1 2.124 (5) 2.113 (7) 1.983 (IO) 2.113 (12) 2.230 (7) M-C2 2.244 (5) 2.244 (5) 2.137 (11) 2.252 (7) M-C7 1.780 ii3j 1.901 (7) M-C8 1.900 (6) 1.755 (13) 1.898 (6) 1.904 (7) M-C9 1.922 (5) 1.941 (7) 1.765 (12) M-C10 1.432 (10) 1.448 (8) 1.432 (21) Cl-C2 1.459 (8) 1.429 (22) 1.468 (10) C2-C3 1.350 (11) 1.348 (8) 1.305 (25) c3-c4 1.429 (12) 1.438 (9) 1.428 (24) c4-c5 1.342 (9) 1.344 (23) 1.358 (11) C5-C6 1.462 (10) 1.455 (8) 1.421 (24) C6-C7 1.425 (11) 1.439 (8) 1.412 (22) C7-Cl 1.161 (8) 1.154 (6) 1.130 (15) C8-01 1.142 (9) 1.155 (7) C9-02 1.163 (15) 1.146 (6) C10-03 1.139 (8) 1.138 (14) . , Bond' Angles C2-M-C1 41.3 38.4 (3) 38.6 (2) C3-M-C2 69.8 66.8 (3) 66.7 (2) 39.7 37.9 (3) 38.3 (2) C7-M-C1 C8-M-C9 97.6 94.9 (3) 94.6 (2) C9-M-C10 104.8 108.6 (3) 108.0 (2) 106.6 106.8 (3) 106.7 (2) C10-M-C8 Cl-C2-C3 126.2 (5) 127.9 125.4 (7) c2-c3-c4 130.3 (6) 131.7 130.8 (7) 127.3 (6) 125.9 126.9 (7) c3-c4-c5 127.6 (6) 127.9 128.4 (7) C4-C5-C6 130.5 (6) 130.3 129.0 (7) C5-C6-C7 126.3 (5) 128.8 127.4 (7) C6-C7-C1 117.5 (5) 117.1 119.4 (6) C7-Cl-C2 177.3 (5) 175.8 176.2 (6) M-C8--01 178.7 (5) 177.4 177.8 (6) M-C9-02 179.1 175.8 (6) 176.9 (5) M-C10-03 "From ref 7. *From ref 11.
isostructural* The found to be isomorphous and unit cell contains Well-seParated Ph&+ cations and (C7H7)M(C0)3-anions. Two perspective views of the anionic organometallic constituent are shown in Figure 1 which also establishes the numbering system. Important bond distances and angles, together with those of la for comparison, are listed in Table IV. It is clear from the figure that the CYClohePtatrienYl ring is bonded to the metal in an q3-fashion in both complexes. This type of structure has already been seen for the analogous iron compound la and its stability over the alternative q4bonded cycloheptatrienyl form (see A and B) has also been predicted on the basis of extended Huckel MO calcula-
Organometallics, Vol. 9, No. 1, 1990 187
Solid-State Structure of (q3-C7H7)M(c0),Table V. 'H and compd
Hl/Cl
H2/C2
NMR Data of the q3-C7H7Ligand in 1 and Fklated Complexes" H3/C3 H,/C4 temp, "C 'H av T,,OC
la -115
-150b -115 -65
95.2 92.8 89.2
-140 -94
5.63d 5.00
-110d -10
103.gd 97.3
lb 2.19 37.9 2.10 3.39 61.7
IC
3c 4e
3.83 37.9 4.27 4.40 51.9
6.42 142.0 6.00 5.98 133.9
4.87 111.9 5.00 5.19 119.3
av
4.90 4.58 4.66
"Chemical Shifts (6) in ppm from TMS in THF-d, (unless otherwise noted). bLow-temperaturespectrum recorded as the PPN' salt in a mixture of CHF2C1/CD2Cl2(4:1).'% e 3 is (q3-C7H7)Co(C0),,spectrum in CF2C12.'3b Hager, D., Edelmann, F., Takats, J., unpublished results. 4 is the symmetrical isomer of (q3-C7H7)0s(CO)3SnPh3, spectrum in CDzC12.4C ni
LJJ
02
w
Figure 1. Perspective views of (q3-C7H7)M(CO)
