Organometallics 1984, 3, 1846-1851
1846
91782-18-2; R U ~ ( C O ) ~ ~ ( ~ - A ~ O 91782-19-3; ~ C C F ~ )O, S ~ ( C O ) ~ ~ ( C ~ - Supplementary Material Available: Listings of structure factor amplitudes, thermal parameters, all bond lengths and Ag02CCF3), 91782-20-6; R~~(r-dam),(CO)~(cc-Ago~CCF~), 91782-21-7; RU&CO)~~, 15243-33-1; [Cu(NCCH3),]BF4,15418-29-8; angles, anisotropic thermal parameters, and hydrogen coordinates 64364-79-0;Ag, 7440-22-4;Hg, 7439-97-6;Cu, (28 pages). Ordering information is given on any current masthead Ru8(r-dpm)(CO)lo, 7440-50-8; Ru, 7440-18-8. page.
Preparation and Structure of the [PIFerrocenophane (q5-C5H4ke(CO)Cp)Fe(q5-C5H4bPh,) and Related Compounds Ian R. Butler and William R. Cullen' Chemistry Department, Unlverslty of British Columbia, Vancouver, British Columbia, Canada V6T 1Y6 Received April 5, 1984
Reaction of (1,l'-ferrocenediy1)phenylphosphinewith phenyllithium in diethyl ether at -78 "C followed by treatment of the product mixture with Fe(CO)&pI gives a number of compounds including the ferI I rocenophanes (q5-C5H4Fe(CO)Cp)Fe(q5-C5H4PPh2) (7) and (q5-C5H4C(0)Fe(CO)Cp)Fe(q5-C5H4PPh2) (8). Treatment of an identical solution with Fe(CO)(PPh3)CpI also gives 7. The reaction of (1,l'femnediy1)phenylarsinewith phenyllithium in a similar manner and subsequent reaction with Fe(CO)zCpI (10). A synthetically useful ferrocenyl byproduct, give primarily (v5-C5H4Fe(CO)zCp)Fe(v5-C5H4AsPh2) (q5-CJ-€41)Fe(q5-C&14PPh2) (61, was also isolated during these syntheses. The crystal and molecular structure of 7 has been determined by single-crystal X-ray diffraction analysis. The crystals are triclinic of space group PT with a = 10.540 (1) A, b = 11.507 (2) A, c = 9.737 ( 3 ) A, (Y = 100.41 (l)", B = 98.49 (1)O, y = 88.95 (l),V = 1148.6 (5) A3, and 2 = 2. The data were refined to R = 0.030 on the basis of 4765 reflections. i
Introduction
A significant number of sigma bonded ferrocene-transition metal complexes of the type 1 are for example, Fp-ferrocene 2,4 which may readily be prepared by reaction of a haloferrocene with NaFp or by reaction of a metalated ferrocene with FpX (X = C1, I; F p = Fe(CO),CP).
QFa
49 1
discovered by Seyferth and WithersloJ1 has proven to be of great synthetic utility in this work (eq 1).
Q - rWh2 PhL,
Fe ,PPh
Fe
4
3
Fe(CO1,Cp
Fe
49
i
2
We have recently been concerned with ligand substitution reactions of 2 using acetylenes and phosphiness and also with the preparation of unsymmetrically, 1,l'-disubstituted ferrocene compounds such as (v5-C5H4PPh2)Fe(q5-C6H4P-t-Bu2)principally for use as ligands in catalysts and catalyst precursors. T h e ring opening reaction of (1,l'-ferrocenediyl)phenylph~sphine~~~ with phenyllithium ~~
~
(1) Cullen, W. R.; Woollins, J. D. Coord. Chem. Rev. 1982, 39, 1. (2)Razuvaev, G.A.; Domrachev, G. A,; Sharutin, V. V.; Suvorova, 0. N. J. Organomet. Chem. 1977,141, 313. (3) Connor, J. A.;Lloyd, J. P. J. Chem. SOC.,Dalton Trans. 1972,1470. Cassias, J. B.; Crawford, G. M.; Flores, A. Inorg. (4) Pannell, K.H.; Chem. 1976,15, 1743. (5) Butler, I. R.;Cullen, W. R.; Rettig, S. J., to be submitted for publication. (6)Butler, I. R.; Cullen, W. R.; Kim, T.-J.;Rettig, S. J., to be submitted for publication. (7) Osbome, A.G.;Whiteley, R. H.; Meads, R. E. J. Organomet.Chem. 1980,193, 345. (8) Osborne, A. G.; Whiteley, R. H.J. Organomet. Chem. 1975,101, C27.
0276-7333/84/2303-1846$01.50/0
It seemed possible that convergence of these two lines of research could result in the preparation of ferrocenophane compounds such as 5 in which intramolecular ligand substitution has occurred. Such compounds would be of interest in view of our previous work and because these would be the first examples of [2]ferrocenophanes with transition metals in the bridge. This paper documents some work in this area utilizing 3 as a key reagent.
9-1 @MLb
5
Experimental Section All reactions were carried out under an inert atmosphere (Ar or Nd using conventional Schlenk techniques. Phenyllithium was supplied by the Aldrich Chemical Co. as a 1.9 M solution in (9) Osborne, A. G.;Whiteley, R. H.; Hollands, R. E. "Proceedings of the Ninth International Conference on Organometallic Chemistry, Dijon, Sept 1979, Abstract 1P14 T. (10) Seyferth, D.; Withers, H. P. J. Organomet. Chem. 1980,185, C1. ( 1 1 ) Seyferth, D.; Withers, H. P. Organometallics 1982, 1, 1275.
0 1984 American Chemical Society
(75-
~ r j i 4 i " e ( ~ o ) c p ) ~CeJ(-+I ~ P P ~ , )
hexane. Fe(C0)2CpIwas prepared from [Fe(CO)zCp]zby the conventional procedure.12 All solvents were predried and freshly distilled. Mass spectra were recorded on a Kratos MS-50 instrument; only the major peaks are reported with relative intensities given in brackets. 'H NMR spectra were obtained by using Bruker WP-80 and WH-400 spectrometers. Microanalyses were performed by Mr. Peter Borda of this department. Reaction of 1'-Lithio-1-(dipheny1phosphino)ferrocene with FpI and Fe(CO)(PPh3)CpI. To a well-stirred diethyl ether solution (ca. 30 mL) of phenyllithium (5 mL, 1.9 M in hexane), maintained at -78 OC by means of a dry ice/acetone bath, was added dropwise (1,l'-ferrocenediy1)phenylphosphine (3,1.18 g, 4.0 "01) in the minimum quantity of ether required for complete solution. Following the addition,the reaction solution was allowed to warm slowly to approximately 0 OC (ca. 5 min) to allow the formation of 4. (The solution becomes clear orange, and this reaction may be monitored by TLC (hexane eluant)). The solution was then rechilled (-78 "C) before adding the appropriate transition-metal complex (9.5 mmol). The resulting solution was allowed to warm slowly to room temperature and then stirred for a further 30 min. Following fiitration to remove the precipitated lithium iodide and insoluble byproducts, the reaction mixture was examined by TLC (90/10 hexane/diethyl ether) and worked up as described below. (i) FpI Reaction. Following TLC examination, which showed the presence of four colored compounds, the solvent volume of the reaction mixture was reduced under vacuum to c& 4 mL. The resulting oil was then chromatographed on a neutral alumina (activity grade 1) column, and the fractions were eluted by using progressively polar mixtures of n-hexane, diethyl ether, and di~hloromethane.'~Each of the four fractions were collected. The first yellow fraction, eluted with 50/50 hexanefdiethyl ether and obtained in low yield, was identified as 6 by comparison with an authentic sample obtained as described below. The second fraction, eluted with 80/20 diethyl ether/hexane as an orange band, gave red needles identifed as 7 after solution concentration and crystallization (from hexane) (30% yield based on the ferrocenophane). 7: 'H NMR (CDC13)6 7.25-7.75 (br m, 10 H), 4.77 (m, 2 H), 4.42 (m, 7 H), 4.48 (8, 5 H, free Cp), 4.30 (m, 2 H), 4.05 (m, 1 H), 3.88 (m, 1 H); IR (CDC13) vm 1927 cm-',(cyclohexane)1917 cm-'; mass spectrum,m / e 518 (M', relative intensity 25.89), 419 (34.13), 490 (l00.00), 489 (18.50), 488 (52.34), 487 (43.01), 486 (49.46),410 (16.01), 370 (14.77), 317 (11.41), 304 (58.23), 245 (23.80), 121 (13.32). anal. Calcd for CBH,J?ezOP: C, 64.91;H, 4.44. Found C, 64.27; H, 4.79.
The third (red/brown) fraction eluted with diethyl ether was identified as [Fe(CO)&p], by comparison with an authentic sample. The fourth (yellow) fraction eluted with 50/50 ether/ dichloromethane was identified as 8. 8 was obtained in low (
