4658
Inorg. Chem. 1990,29,4658-4665 Contribution from the Departments of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India, and University of Delaware, Newark, Delaware 19716
Received March 14, 1990
The compound R U ~ ( C O ) ~ ~ ((1) ~ ~has - Tbeen ~ ) ~prepared by refluxing a benzene solution containing Fe3(CO),(p3-Te), and R U ~ ( C O )The , ~ compounds Ru3(C0),(PPh3),(p3-Te), (2) and R U ~ ( C O ) , ~ ( P P ~ ~ ) ((3) ~ , were - T ~ obtained )~ from the room(4) was obtained from the reaction of 1 temperature reaction of 1 with PPh,. Similarly, Ru~(CO)~(~-P~~PCH,PP~,)(~~-T~), with Ph2PCH2PPh2at room temperature. The structure of 1-4 were established by sin le-crystal X-ray diffraction analysis. Crystal data: 1, orthorhombic, Pccn, a = 6.924 (2) A, b = 16.289 (6) A, c = 18.054 (6) V = 2036 (1) A3, Z = 4, R(F) = 4.16%; 2, monoclinic, P21/n, a = 10.539 (4) A, 6 = 27.39 (1) A, c = 20.415 (7) A, j3 = 94.96 (3)O, V = 5870 (4) A', Z = 4, R(F) = 4.96%; 3,orthorhombic, Pbca, a = 19.070 (5) A, b = 18.157 (4) A, c = 19.272 ( 5 ) A, V = 6673 (3) A3,Z = 8, R(F) = 3.65%; 4, triclinic, Pi, a = 13.255 (3) A, b = 17.610 ( 5 ) A, c = 19.189 ( 5 ) A, a = 65.39 (2)O, 6 = 78.25 (2)O, y = 84.13 (2)O, V = 3986 (2) A', Z = 4, R ( F ) = 2.97%.
1,
Introduction In recent years the chemistry of transition-metal, non-metal cluster compounds has undergone rapid developments; the activity has been particularly high for metal-chalcogen clusters.lq2 The incorporation of main-group elements into transition-metal carbonyl clusters introduces novel structural and reactivity features. Single-atom, main-group-element ligands are being increasingly used as bridges between different metal fragments in cluster growth reactions. The main-group elements often have a key role in stabilizing the bonding network in the transition-metal, nonmetal clusters. Consequently, these clusters often have the ability to add or remove ligands or electrons while retaining the cluster integrity. The triply bridging sulfido ligand has been extensively used for the purpose of cluster growth and stabilization In particular, the numerous sulfidmmium carbonyl clusters obtained systematically by stepwise addition of metal carbonyl units to the p3-S ligands demonstrate the importance of this type of ligand. The much larger tellurium has also been used as a bridge between different metal fragments in cluster synthesis, but indications are that the tellurium-containing clusters will be structurally and chemically different from those containing s ~ l f u r . ~In* ~contrast to the S and Se analogues, Fe3(CO)9(p3-Te)2reacts'with a variety of Lewis bases (L) to form adducts to the form (C0)6Fe2(p3Te)2Fe(CO)3L.6 W e have shown that the Fe(CO),L fragment in t h e adduct is susceptible to replacement by "M(PPh3)2" (M = Ni, Pd, Pt) units to form the mixed-metal complexes (C0)6Fe2(p3-Te)2M(PPh3)2.7 Such transmetalation reactions should provide a simple route to mixed-metal cluster compounds. In this paper, we describe the preparation of Ru,,(CO),,,(pC O ) ( P , - T ~ ) and ~ its reactivity toward triphenylphosphine and bis(dipheny1phosphino)methane. These compounds are believed t o be the first examples or ruthenium clusters with bridging tellurium ligands to be structurally characterized.
Experimental Section All manipulations were carried out under an atmosphere of pure argon
with use of standard Schlenk techniques. Solvents were purified, dried,
and distilled under argon prior to use. Fe3Te2(CO), was prepared by an established procedure.6 Infrared spectra were recorded on a Nicolet SDXB FTIR spectrometer as solutions in dichloromethane in NaCl cells. Prepantion of RII~(CO),~(~-CO)(~~~-T~)~ (1). A mixture of Fe3~ g, 0.295 (CO),(p,-Te), (0.1 g. 0.148 mmol) and R U , ( C O ) ~(0.189 mmol) in 90 mL of benzene solvent was refluxed for 6 h. The solvent was removed in vacuo, and the brown residue was chromatographed on a silica gel column. Elution with hexane separated trace amounts of unreacted Fe,(CO)9(p3-Te), and R U , ( C O ) ~ ~Further . elution with a 7525 mixture of hexane and dichloromethane gave the red product, R U , ( C O ) ~ ~ ( ~ - C O ) ( ~(yield ~ - T ~0.023 ) , g, 8%. based on the amount of 'Indian Institute of Technology. 'University of Delaware.
RU,(CO),~consumed). IR (CH,CI,; u(CO), cm-I): 2087 (w), 2044 (s), 2026 (m), 1989 (m),and 1827 (w). Reaction of RII~(CO)~~(~-CO)(~~-T~), with Tripbenylphospbine. Triphenylphosphine (380 mg, 1.45 mmol) was added to 80 mL of a ~ ~ -mg, T ~ 0.104 ) ~ mmol). CHzCIzsolution of R U , ( C O ) ~ ~ ( ~ - C O ) ((100 The solution was stirred at room temperature for 12 h. Removal of the solvent and chromatography of the residue on silica gel TLC plates using a 70:30 mixture of hexane and dichloromethane separated the following (3) (yield products: yellow-brown RU~(CO)~(~-CO)~(PP~~)(~~-T~)~ 0.002 g, 3%) (1R (CH,CI,; v(CO), cm-I): 2062 (w), 2025 (s), 1997 (w), 1973 (w. sh), 1856 (w), and 1825 (w)); pink R U , ( C O ) ~ ( P P ~ ~ ) , ( ~ , - T ~ ) ~ (2) (yield 0.028 g, 21%) (IR (CH,CI,; u(CO), cm-I): 2027 (sh), 1987 (s), 1957 (s), and 1943 (sh)). Reaction of RU,(CO),~(~~-CO)(~,-T~), with Bis(dipknylphospkin)methane (dppm). A mixture of Ru4(CO)lo(p-CO)(p4-Te)2(190 mg, 0.196 mmol) and dppm (100 mg, 0.260 mmol) dissolved in 75 mL of dichloromethane was stirred at room temperature for 10 h. Removal of the solvent and chromatography of the residue on silica gel column with a 65:35 mixture of hexane and dichloromethane gave a single yellow band of R~,(CO)~(p-CO)(p-dppm)(p~-Te), (4) (yield 0.032 g, 32%). IR (CH,CI,; v(CO), cm-I): 2040 (m), 2009 (s), 1964 (m), and 1790 (w). Crystal Structure Determinations for 1-4. Crystallographic data are collected in Table I. Suitable crystals were obtained from methylene chloride/hexane mixtures and mounted on glass fibers. For 1-3 systematic absences in the diffraction data uniquely determined the space group. For 4, the centrosymmetric alternative was initially assumed and later verified by the chemically reasonable results of refinement. All data sets were empirically corrected for absorption and Lp effects. The structures were solved by direct methods and completed by subsequent difference Fourier syntheses. The asymmetric unit for 1 consists of a half-molecule on a 2-fold axis passing through 0(2), C(2), and the midpoints of the Ru(1)-Ru( la), Ru(2)-Ru(2a), and Te-Te vectors. Two crystallographically independent, but chemically similar, molecules
K. H. J . Coord. Chem. 1988, 17,95. (b) Roberts, D. A.; Geoffroy, G. L. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G.A., Abel, E., Eds.;Pergamon: Oxford, England, 1982;Chapter 40. (c) Huttner, G.; Knoll, K.Angew. Chem., Int. Ed. Engl. 1987,26,743. (d) Vahrenkamp, H. Adv. Organomet. Chem. 1983,22, 169. (e) Herrmann, W. A. Anzew. - Chem., Int. Ed. Engl. 1986, 25, 56. (2) (a) Adams, R. D. Polyhedron 1985,4,2003.(b) Adams, R. D.; Babin, J. E.; Mathur, P.; Natarajan, K.;Wang, J.-W. Inorg.Chem. 1989,26, 1440. (c) Adams, R. D.; Wang, J.-G. Polyhedron 1989, 8, 1437. (3) . . Adams. R. D.: Babin. J. E.:Estrada.. J.:. Wann. _. J.G.: . Hall.. M.B.: . Low.. A. A. Polyhedron 1989.8. 1885. (4) (a) Day, V. W.; Lesch, D. A.; Rauchfuss,T. B. J. Am. Chem. Sor. 1982, 104, 1290. (b) Bogan, L. E., Jr.; Rauchfuss, T. B.; Rheingold, A. L. J . Am. Chem. Soc. 1985,107,3843.(c) Lesch, D. A.; Rauchfuss, T. B. Inorg. Chem. 1983.22, 1854. (d) Bogan, L. E.,Jr.; Rauchfm, T. B.; Rheingold, A. L. Inorg. Chem. 1985,24,3722. (e) Rheingold. A. L.; Acta. Crystallogr., Sect. C 1987,C43, 585. (f) Mathur, P.; Mavunkal, 1. J.; Rheingold, A. L. J . Chem. Soc.. Chem. Commun. 1989, 382. ( 5 ) Mathur, P.; Mavunkal, I. J.; Rugmini, V. Inorg. Chem. 1989,28,3616. ( 6 ) Luch, D. A.; Rauchfuss. T. B. Organometallics 1982,I , 499. (7) (a) Mathur, P.; Mavunhl, I. J. J. Organornet.Chem. 1988. 350,251. (b) Mathur, P.; Mavunkal, I. J.; Rugmini, V. J . Organomer. Chem. 1989,367, 243. (1) (a) Whitmire,
0020-1 669/90/ 1329-4658%02.50/0 0 1990 American Chemical Society
Te-Containing Ru Clusters
Inorganic Chemistry, Vol, 29, No. 23, 1990 4659
Table 1. Crystallographic Data for 1-4 formula fw space group a, A
b, A
c, A a , deg
1
2
R u J e 2 ( W II 967.58
CSOH4506P3RU3Te2
Pccn
6.924 (2) 16.389 (6) 18.054 (6)
v, A3
2 D(caIc), g/cm3 9(Mo Ka), cm-l
temp, OC T(max)/ T(min) radition (A, A) R(F), R,(F),
w 10.539 (4) 27.39 (1) 20.415 (7)
4
CzsH15010PR~4Te2 1201.84
C34H2209RU4Te4 1295.93
Pbca
PI
19.070 (5) 18.157 (4) 19.272 (5)
13.255 (3) 17.610 (5) 19.189 (5) 65.39 (2) 78.25 (2) 84.13 (2) 3986 (2) 4 2.162 30.72 23 1.25
94.96 (3)
B. deg
79 deg
1513.27
3
2036 ( I ) 4 3.157 58.16 23 1.55
5870 (4) 4 1.716 20.99 23 1.10
4.16 4.48
4.96 5.24
Table 11. Atomic Coordinates (XIO') and Isotropic Thermal Parameters (A2 x 103) for 1 Te X Y Z Lp Te 75.5 (6) 7079.8 (3) 2647.4 (3) 28.2 (2) 30.8 (2) Ru(1) 1739.8 (9) 8298.4 (3) 3493.1 (3) 26.9 (2) Ru(2) 1708.2 (8) 8338.9 (3) 1900.9 (3) 9739 (4) O(1) 3685 (12) 4235 (5) 80 (3) 2500 7500 O(2) 4977 (6) 88 (5) -2020 (IO) 8785 (5) O(3) 4204 (5) 82 (3) 9940 (7) O(4) 260 (18) 2508 (5) 87 (4) 9188 (5) O(5) 4205 ( 1 1 ) 754 (4) 74 (3) -1503 (13) 8282 (6) 765 (6) 1 1 1 (5) O(6) 9187 (5) C(1) 2938 (13) 3950 (5) 44 (3) 2500 7500 C(2) 4319 (7) 48 (4) 8615 (6) C(3) -629 (13) 3935 (5) 48 (3) 9304 (5) C(4) 898 (IS) 2413 (5) 46 (3) 3281 (12) 8880 (5) C(5) 1185 (5) 43 (3) -336 (14) 8313 (6) C(6) 1192 (6) 57 (3) a Equivalent isotropic LI defined as one-third of the trace of the orthogonalized U,, tensor.
6673 (3) 8 2.394 24.71 23 1.71 Mo K a (0.71073) 3.65 3.94
2.97 3.21
Tibk 111. Bond Distances and Angles for 1
(a) Bond Distances (A) 2.758 (1) Te-Ru(2) 2.753 (1) Te-Ru(2A) 2.877 (1) Ru(l)-C(I) 2.046 (9) Ru(l)-C(3) 2.753 (1) Ru(l)-Ru(lA) 1.909 (9) Ru(2)-C(5) 1.908 (10) Ru(Z)-Te(A) 2.945 (1) O(l)-C(l) 1.188 (16) 0(3)-C(3) 1.139 (14) O(S)-C(S) 1.119 (14) (b) Bond A Ru( l)-Te-Ru(2) 63.6 (1) Ru(Z)-Te-Ru( 1A) 96.4 (1) Ru( 2)-TtRu(ZA) 66.2 (1) Te-Ru( l)-Ru(2) 57.3 (1) Ru(Z)-Ru(l)-C( I ) 115.3 (3) Ru(Z)-Ru( 1)-C( 2) 138.1 (2) 93.9 (3) Te-Ru( 1)-C(3) 89.3 (4) C( l)-Ru( 1)-C(3) 82.3 (1) Te-Ru( 1)-Te(A) 93.6 (3) C( I)-Ru( l)-Te(A) 171.0 (3) C(3)-Ru( 1)-Te(A) Ru(Z)-Ru(l)-Ru( 1A) 91.4 (1) C(Z)-Ru(l)-Ru( 1A) 46.7 (2) Te(A)-Ru( I)-Ru( 1A) 59.5 (1) TtRu(2)
