2068
Organometallics 1991, 10, 2068-2071
with the results summarized in Table 111.
Acknowld~ent- we thankthe Natural Sciences and Endneering Research Council of Canada, the Ministry of Colleges and Universities of Ontario, and Nova/Polysar Ltd. for financial support of this work.
Supplementary Material Available: Complete lists of bond lengths and angles and tables of H atom coordinates and ieotropic thermal parameters and heavy-atom anisotropic thermal parameters for compound 4 (5 pages); a table of structure factors for compound 4 (12 pages). Ordering information is given on any current masthead page.
Notes Molecular and Crystal Structure of 2,2’,5,5‘-TetramethyI-1,1’-dlstlbaferrocene: A Short Sb-Sb Contact
Inter-Ring
Arthur J. Ashe III,*gt Timothy R. Diephouse,+Jeff W. Kampf,t and Samir M. AI-Taweel$ Department of Chemistty, The University of Michigan, Ann Arbor, Michigan 48 109- 1055, and The Natural Science Department, Mu’tah University, AI Karak, Jordan Received October 3 1, 1990
Summary: 2,2‘,5,5’-Tetramethyl-l, 1‘distibaferrocene (13) was obtained from the reaction of l-phenyl-2,5dimethylstibole with lithium followed by FeCI,. Red crystals of 13 form In Pc space group with Z = 2, a = 6.81 1 (1) A, b = 11.336 (3) A, c = 8.918 (3) A, and fl = 102.80 (2)’. The full structure has been determined and shows a ferrocene-like arrangement with a close (3.68 A) inter-ring S b 4 b contact.
The group 15 heterobenzenes 1-5 are an important series in which elements of an entire column of the periodic table have been incorporated into aromatic The com-
a similar series that can be compared with the heteroand $14 have been benzenes. Derivatives of 6,’ 7,%1° reported. Prior structural data are available for 3,3’,4,4’-tetramethyl-1,l’-diphosphaferrocene (I 1)9 and 2,2’,5,5’-tetramethyl-l,l’-diarsaferrocene (12).12 We report here on the crystal and molecular structure of 2,2’,5,5’tetramethyl- 1,l’-distibaferrocene ( 13).
Results and Discussion Compound 13 was prepared by a route modified compared to that previously reported.14 The exchange reaction of phenylantimony dichloride with l,l-dibutyl-2,5-dimethylstannole (14)gave a 63% yield of l-phenyl-2,5-di-
14
6E-N
7
P
11
12
1s
13
8 A s 9 10
%
Bi
parison of properties, particularly structural properties,” of 1-5 has provided insight into the concepts of aromaticity and *-bonding between carbon and the heavier main-group The group 15 diheteroferrocenes 6-10 form ~
~~
University of Michigan.
* Mu’tah University.
(1) Jutzi, P . Angew. Chem., Int. Ed. Engl. 1976,14, 232. (2) Ashe, A. J., 111. Acc. Chem. Res. 1978, 11, 153. (3) Ashe, A. J., 111. Top. Curr. Chem. 1982, 105, 125. (4) Wong, T. C.; Bartell, L. S. J. Chem. Phys. 1974, 61, 2840. Kuczkowski, R. L.; Ashe, A. J., 111. J. Mol.Spectrosc. 1972, 42, 457. (5) Wong, T. C.; Ashe, A. J., III; Bartell,L. S. J. Mol.Struct. 1975,25, 65. Lnttimer, R. P.; Kuczkowski, R. L.; Ashe, A. J., 111; Meinzer, A. L. J. Mol.Spectrosc. 1971, 57, 428. Wong, T. C.; Ashe, A. J., 111. J. Mol. Struct. 1978,48, 219. (6) Fong, G. D.; Kuczkowski, R. L.; Ashe, A. J., 111. J. Mol. Spectrosc. 1978, 70, 197. Wong, T. C.; Ferguson, M. G.; Ashe, A. J., 111. J. Mol. Struct. 1979, 52, 231.
0276-7333/91/2310-2068$02.50/0
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17
18
(7) King, R. B.; Bisnette, M. B. Inorg. Chem. 1964,3,796. Joshi, K. K.; Pauson, P. L.; Qazi, A. R.; Stubbs, W. H. J. Organomet. Chem. 1964,
1 , 471. (8) Abel, E. W.; Towers, C. J. Chem. SOC.,Dalton Trans. 1979,814.
(9) delauzon, G.; Deschamps, B.; Fiecher, J.; Mathey, F.; Mitachler, 1980,102,994. Mathey, F.; Mitschler, A.; Weise, A., J. Am. Chem. SOC. R.J . Am. Chem. SOC.1976,99, 3537. (10) Lemoine, P.; Gross, M.; Braunstein, P.; Mathey, F.; Deschamps, B.; Nelson, J. H. Organometallics 1984, 3, 1303 and references cited therein . (11) Thiollet, G.; Mathey, F.; Poilblanc, R. Inorg. Chim. Acta 1979,32, L67.
(12) Chiche, L.; Galy, J.; Thiollet, G.; Mathey, F. Acta Crystallogr. 1980, B36, 1344. (13) Ashe, A. J., III; Mahmoud, S.; Elschenbroich, C.; Whsch, M. Angew. Chem., Int. Ed. Engl. 1987,26, 229. (14) Ashe, A. J., III; Diephouse, T. R. J.Organomet. Chem. 1980,202,
c95.
0 1991 American Chemical Society
Organometallics, Vol. 10, NO.6, 1991 2069
Notes Table I. Summary of Cwstalloeraehic Data for 13 Crystal Data empirical formula Cl2Hl6FeSb2 fw 459.608 deep red irregular fragment cryst color and habit 0.20 X 0.42 X 0.30 mm cryst dimens cryst system monoclinic Pc (No. 7)" space group z 2 unit cell dimens from 25 reflcns (22.8' 5 20 I 38.5') a 6.811 (1) A b 11.336 (3) A C 8.918 (3) A 102.80 (2)' B V 671.4 (3) A3 2.27, g cm" d (calcd) 432 electrons F(O00) linear abs coeff ( p ) 50.56 cm-' Data Collection diffractometer Syntex P21 radiation type Mo Ka, X = 0.710 73 A, Lp corrected, graphite monochromator ambient temp Ol20 scan scan type 5-52' 28 scan range +h,+k,il (h,019; k, 0114; 1,12112) octants used plus Friedel pairs scan rate 1.5-5' min-I, variable scan width 1.0' below K q to 1.0' above Kaz bkgdlscan ratio 0.5 std reflcns 3 measd every 100 reflcns, linear decay -3% no. of data collcd 3153 no. of unique reflcns 2651, Rbt = 0.0741 abs cor emDirical. 6 scans R merge beforelafter cor O.Obl5/0.0300 max/min transm 0.23610.199 Solution and Refinement Siemens SHELXTL PLUS, VAXStation 3500 solution Patterson refinement method full-matrix least-squares function minimized CW(F, - Fc)2 H atoms riding model, dc-H= 0.96 A, common isotropic U(H)refined to 0.12 (2) A2 no. of refined reflcns with F, 2645 L 0.6u(F) no. of params refined 136 data/param ratio 19.4 0.0399 R = E(IFol - lFcl)/XlFol) 0.0530 R" = [X(IFd - lFcl)2 syst used
lZ~lFOl~l"2
+
(ur- = $(FA 0.003431(F0j2) GOF mean shiftlerror max shiftlerror secondary extinction resid electron dens
0.90
