Organometallics 1993,12, 406412
408
Study on the Reaction between Metal-Metal-Bonded Compounds [(q5-RC5H4)M(CO)& and Cop(CO)s. Synthesis and Characterization of the Tetrahedral Clusters (q5-RC~H4)M(CO)2Co3(CO)G(CL-CO)3 (M = Mo, W; R = Me3Si, C(O)Me, COzMe, C02Et) Li-Cheng Song,* Jin-Yu Shen, and Qing-Mei Hu Department of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
Ru-Ji Wang and Hong-Gen Wang Central Laboratory, Nankai University, Tianjin 300071, People's Republic of China Received May 13, 1992
Through the reaction of respective dimers [(q5-RC5H4)M(C0)312(la-f) with Coz(CO)a in refluxing toluene, the cluster complexes of (.~~~-RC~H~)M(CO)~CO~(CO)~(~-CO)~ (2a-f) (2a M = Mo, R = Me3Si; 2b M = Mo, R = C02Me; 2c M = Mo, R = C02Et; 2d M = W, R = C(0)Me; 2e M = W, R = C02Me; 2f M = W, R = C02Et),were prepared in 18-32% yields and characterized by C/H analysis, IR, lH NMR and MS spectroscopies. In addition, 2f also could be prepared by reaction of I f with C04(CO)12 in 14% yield. The determination of single-crystal molecular structure of one repesentative, 28, showed that the molecule crystallizes in the triclinic space group PI with a = 8.679 (2) A, b = 9.473 (3) A, c = 13.817 (4) A, CY = 78.31 (3)O, @ = 82.81 (3)O, y = 85.44 (3)", V = 1101.9 (7) A3, and 2 = 2; final R = 0.046 for 3441 observed reflections. Introduction
Results and Discussion
The chemistry of transition metal-metal-bonded comWhen a mixture of bis[q5-substituted cyclopentadiepounds and of metal cluster complexes is of great interest nyltricarbonylmolybdenum(tungsten)l dimers la-f and and has become the subject of a large number of C02(CO)8 are refluxed in toluene for 10 h, the expected For group 6 transition metals, however, only a few metalMCo3 cluster complexes 2a-f were obtained in 1&32% metal-bonded compounds with q5-functionalcyclopentayields (Scheme I). dienyl ligands and the tetrahedral MCo3 (M = Mo, W) Thus, the results demonstrated some generality of this cluster complexes which contain +substituted cyclopenkind of reaction,regardless of the dimers used. The dimers, tadienyl ligands have been Recently, it for instance, may contain either a Mo-Mo or W-W metalwas claimed that reaction of [Cp(C0)3Mol2with Co2(CO)a metal bond and may also carry various substituents on could most conveniently give the clusters of CpMo(C0)zthe cyclopentadienyl ring. However, the second type of CO~(CO)~(P-CO)~ in 25% yield, along with a trace of M&oz cluster complexes were not found in our experiC~MO(CO)~CO~(CO)~MO(CO)C~(~CO)~.~~ In order to ments, which was contrary to the reaction carried out by explore the scope and limitations of this novel reaction Kaganovich and his co-workers.12 and also to make the new MC03 (M = Mo, W) clusters of The cluster complexes 2a-f are air-stable black solids, the type mentioned above, particularlythe type containing but their solutions are quite air-sensitive. The data of q5-functionalcyclopentadienyl ligands, we initiated this combustion analysis,IR, 'H NMR, and MS are consistent study and now report our results. with the structures shown in Scheme 1. In IR spectrum of 2a there are two groups of peaks, one * To whom correspondence should be addressed. (1)Cotpn, F. A,; Wilkinson, G. Advanced Inorganic Chemistry, 4th between 2078 and 1949 cm-l and the other ranging from ed.;JohnWiley&Sons: NewYork,1980;pp1080-1112(seealsoreferencea 1882 to 1822 cm-', both characteristic of terminal and therein). (2)Cotton, F. A.; Chisholm, M. H. Chem. Eng. News 1982,60,40. bridging carbonyls. However, for 2b-f there are three (3)Roberta, D. R.; Geoffroy, G.L. In Comprehensive Organometallic kinds of peaks, one around 1700 cm-', indicating the Chemistry; Willkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon existence of an ester or acyl carbonyl,the other two in the Press: Oxford, England, 1982;Vol. 6,pp 763-877 (see also references therein). regions 2082-1926 and 1885-1818 cm-l, also characteristic (4) Chaloyard, A,; Murr, N. E. Inorg. Chem. 1980,19,3217. of terminal and bridging carbonyls, respectively. For lH ( 5 ) Edelmann, F.;Tdfke, S.;Behrens, U. J. Organomet. Chem. 1986, NMR assignment of 2b-f, it is evident that the downfield 309, 87. (6)Medina, R. M.; Maeaguer, R. J.; MorBn, M.;Losada, J. Inorg. Chim. apparent triplet should be assigned to protons H(2) and Acta 1988,146,115. H(5) and the upfield triplet to H(3)and H(4), but inversely (7) Song, L X . ; Yang, H.; Dong, Q.; Hu,Q.-M. J. Organomet. Chem. 1991,414,137. for 2a, since the substituents of the acetyl and ester groups (8)Song, L.4.; Dong, Q.; Hu,Q.-M. Acta Chim. Sin. 1992,50, 193. on cyclopentadienyl ring are well-known electron-with(9)Avey, A.; Tenhaeff, S. C.; Weakley, T. J. R.; Tyler, D. R. drawing groups and the Me& substituent is an electronOrganometallics 1991,10, 3607. (10)Song, L.-C.; Shen, J.-Y, Chem. J. Chin. Uniu. 1992,13,1227. releasing g r 0 ~ p . l ~ (11)Chetcuti, M. J.; Gordon, J. C.; Fanwick, P. E. Inorg. Chem. 1990, 29,3781. (12)Kaganovich, V. S.;Slovakhotov, Yu. L.; Mironov, A. V.; Struchkov, Yu.T.; Rybinskaya, M. I. J. Organomet. Chem. 1989,372,339.
(13)Macomber, D. W.; Rausch, M. D. J. Organomet. Chem. 1988,258, 331.
0276-7333/93/2312-0408$04.00/0 0 1993 American Chemical Society
Tetrahedral Clusters (~-RC~~)M(CO),CO,(CO)~(C~-CO),
Table 11. Bond Distances (A) between Non-Hydrogen Atoms for k.
Scheme I
+
Organometallics, Vol. 12, No. 2, 1993 409
toluene cor(c0)s
Table I. Fractional Coordinates and Equivalent Isotropic Thermal Parameters of Non-Hydrogen Atoms for 2e atom X Y 2 B, (A2) 0 5 4 1 6 (5) 0.7105 (2) 0.9226 (2) 0.6449 (2) 0.818 (1) 0.833 (1) 0.560 (1) 0.4374 (9) 0.667 (1) 0.636 (1) 0.680 (1) 0.655 (1) 1.084 (1) 1.1 89 (1) 0.998 (2) 1 .OS4 (2) 0.534 (1) 0.465 (1) 0.577 (2) 0.528 (2) 0.514 (1) 0.382 (1) 0.937 (1) 1.027 (1) 0.835 (1) 0.866 (1) 0.818 (1) 0.966 (1) 1.009 (1) 0.888 (1) 0.765 (1) 0.733 (1) 0.603 (1) 0.8216 (9) 0.754 (2)
0.30370 (4) 0.3988 (2) 0.2078 (2) 0.1515 (2) 0.106 (1) 4.0123 (9) 0.294 (1) 0.2896 (9) 0.579 (1) 0.698 (1) 0.402 (2) 0.395 (1) 0.161 (1) 0.124(1) 0.175 (1) 0.154 (2) 0.034 (1) -0.042 (1) 0.095 (2) 0.064 (2) 0.336 (1) 0.372 (1) 0.411 (1) 0.501 (1) 0.023 (1) 4.1006 (9) 0.385 (1) 0.337 (1) 0.430 (1) 0.534 (1) 0.508 (1) 0.339 (1) 0.3823 (9) 0.255 (1) 0.221 (2)
0.34878 (4) 0.1607 (1) 0.1856 (1) 0.2395 (1) 0.4197 (8) 0.4692 (8) 0.407 (1) 0.4467 (7) 0.168 (1) 0.173 (1) 0.034 (1) -0.0427 (8) 0.252 (1) 0.294 (1) 0.066 (1) -0.010 (1) 0.3358 (9) 0.3951 (8) 0.139 (1) 0.075 (1) 0.216 (1) 0.2288 (8) 0.142 (1) 0.1171 (8) 0.233 (1) 0.250 (1) 0.4871 (9) 0.4499 (8) 0.3566 (9) 0.337 (1) 0.417 (1) 0.588 (1) 0.61 18 (7) 0.6490 (7) 0.752 (1)
2.155 (7) 2.83 (3) 2.93 (3) 2.76 (3) 3.2 (2) 4.6 (2) 3.2 (2) 4.0 (2) 4.1 (3) 6.6 (3) 4.4 (3) 6.5 (3) 4.1 (3) 6.2 (3) 5.0 (4) 10.2 (4) 3.3 (3) 4.9 (2) 5.6 (4) 12.6 (4) 4.0 (3) 5.0 (2) 3.4 (3) 4.8 (2) 3.4 (3) 5.7 (3) 2.8 (2) 2.7 (2) 3.0 (2) 3.2 (2) 3.4 (3) 3.2 (2) 4.1 (2) 3.9 (2j 5.2 (4)
The 70-eV E1 mass spectra of 2a-f did not show their respective molecular ion but showed the fragment ions RC~H~MCO~(CO),+ (n= 0-6)and MCO~(CO),+ (h= &7), both resulting from parent molecular ions by successive loss of a given number of carbonyls and the substituted cyclopentadienyl. In order to unambiguously confirm the structures of 2a-f, the molecular structure of 26 was determined by single-crystal X-ray diffraction. The finalfractionalcoordinateswith equivalent isotropic thermal parameters are listed in Table I. Tables I1 and I11 list the bond lengths and bond angles, respectively. The perspective view of 2e is presented in Figure 1. As seen from Figure 1, the molecule has a tetrahedral core MC03, which carries eight terminal carbonyls [each twobeingonCo(l),Co(2),Co(3),and W(l)I, threebridging carbonyls [each across Co(l)-Co(2),co(2)-Co(3),and Co(1)40(3)1,and an q5-MeO&C5H4 ligand bonded to the W atom. Thus, the molecular structure of 2e is similar to
W(1 )-C(l) W(1 )-CW W(l)-C(21) CO(1)-W(l) Co(l)-C0(2) co(l)-Co(3) CO(~ ( 3 ) C0(2)-W(l) C0(2)-Co(l) c0(2)
