Abstract
Reactions of [Ni6(CO)12]2- (1) with CuBr2 have given rise in small yields (∼10%) to the first example of a close-packed copper-nickel carbonyl cluster; its formulation as [CuxNi35-x(CO)40]5- (with x=3 or 5) is based upon a low-temperature CCD X-ray crystallographic determination coupled with an elemental analysis and X-ray fluorescence measurements. This air-unstable black pentaanion (2) together with one co-crystallized bromide anion, six [NMe4]+ counterions, and one solvated acetone molecule comprise the crystallographic independent part in a monoclinic unit cell of P21/n symmetry (with Z=4). The geometrically unprecedented 35-atom hcp M(A)2M(B)3Ni30 polyhedron of pseudo-D3h symmetry consists of a central 15-atom equilateral ν4M(B)3Ni12 triangle that is capped on both sides by two symmetry-related 10-atom equilateral ν3M(A)Ni9 triangles. The 35-atom M(A)2M(B)3Ni30 core is encapsulated by 40 COs, whose connectivities, due to an “extra” CO ligand on one of the three triangular sides, reduce the pseudo D3h symmetry of the metal core to Cs. An elemental analysis via AA and X-ray fluorescence measurements resulted in Cu/Ni ratios of 3.2/31.8 and 3.7/31.3, respectively, that are consistent with the metal core being either Cu5Ni30 (i.e., M(A)=M(B)=Cu) or Cu3Ni32 (i.e., M(A)=Ni; M(B)=Cu). Several attempts to determine the actual stoichiometry of the metal core by use of electrospray FT/MS/ICR measurements were unsuccessful. The maximum metal-core diameter of 2 is ca. 0.41 nm parallel and 0.85 nm perpendicular to the principal 3-fold axis.
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REFERENCES
Selected articles with references are (a) J. H. Sinfelt, Bimetallic Catalysts: Discoveries, Concepts, and Applications (Wiley, New York, 1983). (b) V. Ponec (1983). Adv. Catal. 32, 149. (c) W. M. H. Sachtler and R. A. van Santen (1977). Adv. Catal. 26, 69. (d) J. H. Sinfelt (1987). Acc. Chem. Res. 20, 134. (e) W. M. H. Sachtler and A. Yu. Stakheev (1993). Catal. Today 12, 283. (f ) B. C. Gates, Catalytic Chemistry (Wiley, New York, 1992). (g) P. Braunstein and J. Rose, in E. W. Abel, F. G. A. Stone, and G. Wilkinson (eds.), Comprehensive Organometallic Chemistry II (Elsevier, Tarrytown, New York, 1995), Vol. 10, in R. D. Adams (ed.), Chap. 7, p. 351. (h) G. Süss-Fink and G. Meister (1993). Adv. Organomet. Chem. 35, 41. (i) N. Toshima and T. Yonezawa (1998). New J. Chem. 22, 1179. ( j) R. D. Adams and F. A. Cotton (eds.), Catalysis by Di-and Polynuclear Metal Cluster Complexes (Wiley–VCH, New York, 1998). (k) P. Braunstein, L. A. Oro, and P. R. Raithby (eds.), Metal Clusters in Chemistry (Wiley–VCH, New York, 1999), Vol. 2. (l) G. Ertl, H. Knözinger, and J. Weitkamp (eds.), Handbook of Heterogeneous Catalysis (Wiley–VCH, New York, 1994).
G. A. Somorjai, Introduction to Surface Chemistry and Catalysis (Wiley, New York, 1994).
(a) J. A. Rodriguez and D. W. Goodman (1995). Acc. Chem. Res. 28, 477. (b) J. A. Rodriguez (1996). Surf. Sci. 345, 347. (c) J. A. Rodriguez (1996). Heterogen. Chem. Rev. 3, 17. (d) J. A. Rodriguez (1996). Surf. Sci. Rep. 24, 223. (e) J. A. Rodriguez and J. Hrbek (1999). Acc. Chem. Res. 32, 719.
M. Fernández-Garcia, J. C. Conesa, A. Clotet, J. M. Ricart, N. Lopez, and F. Illas (1998). J. Phys. Chem. B. 102, 141.
(a) M. Polak and L. Rubinovich (2000). Surf. Sci. Rep. 38, 127, and references therein. (b) J. H. Larsen and I. Chorkendorff (1999). Surf. Sci. Rep. 35, 163, and references therein.
G. Meitzner, D. A. Fischer, and J. H. Sinfelt (1992). Catal. Lett. 15, 219.
K. Khulbe and R. Mann (1982). Catal. Rev. Sci. Eng. 24, 311.
(a) J. C. Harberts, A. F. Bourgonje, J. J. Stephan, and V. Ponec (1977). J. Catal. 47, 92. (b) C. Benndorf, K. H. Gressmann, J. Kessler, W. Kirstein, and F. Thieme (1979). Surf. Sci. 85, 389. (c) K. Y. Yu, D. T. Ling, and W. E. Spicer (1976). J. Catal. 44, 373. (d) C. R. Helms, K. Y. Yu, and W. E. Spicer (1975). Surf. Sci. 52, 217.
M. T. Tavares, I. Alstrup, C. A. Bernardo, and J. R. Rostrup-Nielsen (1994). J. Catal. 147, 525.
M. T. Tavares, I. Alstrup, C. A. Bernardo, and J. R. Rostrup-Nielsen (1996). J. Catal. 158, 402.
J. Nerlov and I. Chorkendorff (1999). J. Catal. 181, 271.
P. S. Kumbhar, R. A. Rajadhyaksha, and R. Vetrievel (1992). J. Chem. Soc. Faraday Trans. 88, 1165.
(a) L. Zhu and A. E. DePristo (1997). J. Catal. 167, 400. (b) L. Zhu and A. E. DePristo (1995). J. Chem. Phys. 102, 5342. (c) L. Yang and A. E. DePristo (1994). J. Catal. 148, 575. (d) L. Zhu, K. S. Liang, B. Zhang, J. S. Bradley, and A. E. DePristo (1997). J. Catal. 167, 412. (e) L. Zhu, R. Wang, T. S. King, and A. E. DePristo (1997). J. Catal. 167, 408.
(a) J. C. Calabrese, L. F. Dahl, A. Cavalieri, P. Chini, G. Longoni, and S. Martinengo, (1974). J. Am. Chem. Soc. 96, 2616. (b) G. Longoni, P. Chini, and A. Cavalieri(1976). Inorg. Chem. 15, 3025. (c) A. Ceriotti, G. Longoni, and G. Piva (1989). Inorg. Synth. 26, 312.
J. K. Ruff, R. P. White, Jr., and L. F. Dahl (1971). J. Am. Chem. Soc. 93, 2159.
T. Hall and J. K. Ruff (1981). Inorg. Chem. 20, 4444.
A. Ceriotti, R. Della Pergola, G. Longoni, M. Manassero, and M. Sansoni (1984). J. Chem. Soc. Dalton Trans. 1181.
A. Ceriotti, R. Della Pergola, G. Longoni, M. Manassero, N. Masciocchi, and M. Sansoni (1987). J. Organomet. Chem. 330, 237.
A. Ceriotti, R. Della Pergola, L. Garlaschelli, G. Longoni, M. Manassero, N. Masciocchi, M. Sansoni, and P. Zanello (1992). Gazz. Chim. Ital. 122, 365.
A. Fumagalli, G. Longoni, P. Chini, A. Albinati, and S. Brückner (1980). J. Organomet. Chem. 202, 329.
D. A. Nagaki, J. V. Badding, A. M. Stacy, and L. F. Dahl (1986). J. Am. Chem. Soc. 108, 3825.
A. Ceriotti, F. Demartin, G. Longoni, M. Manassero, G. Piva, G. Piro, M. Sansoni, and B. T. Heaton (1986). J. Organomet. Chem. 301, C5.
F. Demartin, C. Femoni, M. C. Iapalucci, G. Longoni, and P. Macchi (1999). Angew. Chem. Int. Ed. Engl. 38, 531.
A. Ceriotti, F. Demartin, G. Longoni, M. Manassero, M. Marchionna, G. Piva, and M. Sansoni (1985). Angew. Chem. Int. Ed. Engl. 24, 697.
J. M. Bemis and L. F. Dahl, unpublished research.
(a) M. Kawano, J. W. Bacon, C. F. Campana, and L. F. Dahl (1996). J. Am. Chem. Soc. 118, 7869. (b) M. Kawano, J. W. Bacon, C. F. Campana, B. E. Winger, J. D. Dubek, S. A. Sirchiö, S. L. Scruggs, U. Geiser, and L. F. Dahl (2001). Inorg. Chem. 40.
M. A. Kozee and L. F. Dahl, manuscript in preparation.
C. Femoni, M. C. Iapalucci, G. Longoni, P. H. Svensson, and J. Wolowska (2000). Angew. Chem. Int Ed. 39, 1635.
N. T. Tran, M. Kawano, D. R. Powell, and L. F. Dahl (2000). J. Chem. Soc., Dalton Trans. 4138.
M. Kawano and L. F. Dahl, submitted for publication.
J. M. Bemis and L. F. Dahl (1997). J. Am. Chem. Soc. 119, 4545.
(a) A. J. Whoolery and L. F. Dahl (1991). J. Am. Chem. Soc. 113, 6683. (b) A. J. Whoolery Johnson, B. Spencer, and L. F. Dahl (1994). Inorg. Chim. Acta 227, 269.
N. T. Tran, M. Kawano, R. K. Hayashi, D. R. Powell, C. F. Campana, and L. F. Dahl (1999). J. Am. Chem. Soc. 121, 5945.
(a) I. D. Salter (1989). Adv. Organomet. Chem. 29, 249. (b) I. D. Salter, in E. W. Abel, F. G. A. Stone, and G. Wilkinson (eds.), Comprehensive Organometallic Chemistry II (Elsevier, Terrytown, New York, 1995), Vol. 10, in R. D. Adams (ed.), Chap. 5, p. 255. (c) I. D. Salter, in P. Braunstein, L. A. Oro, and P. R. Raithby (eds.), Metal Clusters in Chemistry (Wiley–VCH, New York, 1999), Vol. 1, p. 509.
(a) H. A. Mirza, J. J. Vittal, and R. J. Puddephatt (1991). J. Chem. Soc. Chem. Commun. 309. (b) H. A. Mirza, J. J. Vittal, R. J. Puddephatt, C. S. Frampton, L. Manojlovíc-Muir, W. Xia, and R. H. Hill (1993). Organometallics 12, 2767.
M. J. Freeman, A. G. Orpen, and I. D. Salter (1987). J. Chem. Soc. Dalton Trans. 379.
(a) S. S. D. Brown, S. Hudson, and I. D. Salter (1987). J. Chem. Soc. Dalton Trans. 1967. (b) S. S. D. Brown, I. D. Salter, and B. M. Smith (1985). J. Chem. Soc. Chem. Commun. 1439.
(a) G. Doyle, K. A. Eriksen, and D. van Engen (1985). J. Am. Chem. Soc. 107, 7914. (b) G. Doyle, K. A. Eriksen, and D. van Engen (1986). J. Am. Chem. Soc. 108, 445. (c) G. Doyle, B. T. Heaton, and E. Occhiello (1985). Organometallics 4, 1224.
(a) P. Klüfers (1984). Angew. Chem. Int. Ed. Engl. 23, 307. (b) P. Klüfers (1985). Angew. Chem. Int. Ed. Engl. 24, 70.
M. Achternbosch, H. Braun, R. Fuchs, P. Klüfers, A. Selle, and U. Wilhelm (1990). Angew. Chem. Int. Ed. Engl. 29, 783.
(a) J. A. Howard, R. Sutcliffe, and B. Mile (1985). Surf. Sci. 156, 214. (b) B. Zhuang, B. Pan, L. Huang, and P. Yu (1994). Inorg. Chim. Acta. 227, 119.
R. W. Broach, L. F. Dahl, G. Longoni, P. Chini, A. J. Schultz, and J. M. Williams (1978). ACS Adv. Chem. Ser. 167, 93.
A. Ceriotti, P. Chini, R. D. Pergola, and G. Longoni (1983). Inorg. Chem. 22, 1595.
P. Chini, G. Longoni, M. Manassero, and M. Sansoni (1977). Abstracts of the Eighth Meeting of the Italian Association of Crystallography, Ferrara, Commun. 34.
(a) A. F. Masters and J. T. Meyer (1995). Polyhedron 14, 339. (b) J. K. Beattie, A. F. Masters, and J. T. Meyer (1995). Polyhedron 14, 829.
(a) G. Longoni and M. C. Iapalucci, in G. Schmid (ed.), Clusters and Colloids: From Theory to Applications (VCH, New York, 1994), p. 91. (b) A. Ceriotti, R. D. Pergola, and L. Garlaschelli, in L. J. de Jongh (ed.), Physics and Chemistry of Metal Cluster Compounds (Kluwer Academic, Dordrecht, The Netherlands, 1994), Chap. 2, p. 41.
(a) A. Ceriotti, G. Longoni, M. Manassero, N. Masciocchi, G. Piro, L. Resconi, and M. Sansoni (1985). J. Chem. Soc. Chem. Commun. 1402. (b) A. Ceriotti, A. Fait, G. Longoni, G. Piro, L. Resconi, F. Demartin, M. Manassero, N. Masciocchi, and M. Sansoni (1986). J. Am. Chem. Soc. 108, 5370. (c) A. Ceriotti, A. Fait, G. Longoni, G. Piro, F. Demartin, M. Manassero, N. Masciocchi, and M. Sansoni (1986). J. Am. Chem. Soc. 108, 8091.
(a) B. K. Teo and H. Zhang (1990). Polyhedron 9, 1985, and references therein. (b) B. K. Teo, H. Zhang, Y. Kean, H. Dang, and X. Shi (1993). J. Chem. Phys. 99, 2929.
(a) D. M. P. Mingos (1985). J. Chem. Soc. Chem. Commun. 1352. (b) D. M. P. Mingos and L. Zhenyang (1988). J. Chem. Soc. Dalton Trans. 1657.
N. T. Tran, M. Kawano, D. R. Powell, and L. F. Dahl, submitted for publication.
D. A. van Leeuwen, J. M. van Ruitenbeek, L. J. de Jongh, A. Ceriotti, G. Pacchioni, O. D. Häberlen, and N. Rösch (1994). Phys. Rev. Lett. 73, 1432, and references therein.
B. J. Pronk, H. B. Brom, L. J. de Jongh, G. Longoni, and A. Ceriotti (1986). Solid State Commun. 54, 349.
(a) S. H. Strauss (2000). J. Chem. Soc. Dalton Trans. 1, and references therein. (b) J. J. Rack, J. D. Webb, and S. H. Strauss (1996). Inorg. Chem. 35, 277, and references therein. (c) J. J. Rack and S. H. Strauss (1997). Catal. Today 36, 99. (d) K. G. Caulton, G. Davies, and E. M. Holt (1990). Polyhedron 9, 2319, and references therein. (e) E. I. Solomon, P. M. Jones, and J. A. May (1993). Chem. Rev. 93, 2623.
(a) M. R. Churchill, B. G. DeBoer, F. J. Rotella, O. M. Abu Salah, and M. I. Bruce (1975). Inorg. Chem. 14, 2051. (b) M. Pasquali, F. Marchetti, and C. Floriani (1978). Inorg. Chem. 17, 1684. (c) M. Pasquali, C. Floriani, and A. Gaetani-Manfredotti (1981). Inorg. Chem. 20, 3382. (d) M. Pasqueli, G. Marini, C. Floriani, A. Gaetani-Manfredotti, and C. Guastini (1980). Inorg. Chem. 19, 2525. (e) J. S. Thompson and J. F. Whitney (1984). Inorg. Chem. 23, 2813. (f ) L. Stamp and H. T. Dieck (1987). Inorg. Chim. Acta 129, 107. (g) W. Kläui, G. Lenders, B. Hessner, and K. Evertz (1988). Organometallics 7, 1357. (h) H. V. R. Diaz and H.-L. Lu (1995). Inorg. Chem. 34, 5380. (i) C. Lopes, M. Hakansson, and S. Jagner (1997). Inorg. Chem. 36, 3232.
R. L. Geerts, J. C. Huffman, K. Folting, T. H. Lemmen, and K. G. Caulton (1983). J. Am. Chem. Soc. 105, 3503.
(a) R. R. Gagné, J. L. Allison, R. S. Gall, and C. A. Koval (1977). J. Am. Chem. Soc. 99, 7170. (b) R. R. Gagné (1976). J. Am. Chem. Soc. 98, 6709.
M. Pasquali, C. Floriani, G. Venturi, A. Gaetani-Manfredotti, and A. Chiesi-Villa (1982). J. Am. Chem. Soc. 104, 4092, and references therein.
G. Doyle, K. A. Eriksen, M. Modrick, and G. Ansell (1982). Organometallics 1, 1613.
C. D. Desjardins, D. B. Edwards, and J. Passmore (1979). Can. J. Chem. 57, 2714.
S. M. Ivanova, S. V. Ivanov, S. M. Miller, O. P. Anderson, K. A. Solntsev, and S. H. Strauss (1999). Inorg. Chem. 38, 3756.
F. Aubke and C. Wang (1994). Coord. Chem. Rev. 137, 483.
A. S. Goldman and K. Krogh-Jespersen (1996). J. Am. Chem. Soc. 118, 12159.
M. Hakansson and S. Jagner (1990). Inorg. Chem. 29, 5241.
F. Meyer, Y.-M. Chem, and P. B. Armentrout (1995). J. Am. Chem. Soc. 117, 4071.
G. Doyle, K. A. Eriksen, and D. Van Engen (1985). Organometallics 4, 877.
L. Carlton, W. E. Lindsell, K. J. McCullough, and P. N. Preston (1983). J. Chem. Soc. Chem. Commun. 216.
G. Doyle, K. A. Eriksen, and D. Van Engen (1985). Organometallics 4, 2201.
S. S. D. Brown, S. Hudson, I. D. Salter, and M. McPartlin (1987). J. Chem. Soc. Dalton Trans. 1967.
M. L. Buhl, G. J. Long, and G. Doyle (1993). J. Organomet. Chem. 461, 187.
K. Albert, K. M. Neyman, G. Pacchioni, and N. Rösch (1996). Inorg. Chem. 35, 7370.
(a) V. G. Albano, F. Azzaroni, M. C. Iapalucci, G. Longoni, M. Monari, S. Mulley, D. M. Proserpio, and A. Sironi (1994). Inorg. Chem. 33, 5320. (b) V. G. Albano, F. Calderoni, M. C. Iapalucci, G. Longoni, and M. Monari (1995). J. Chem. Soc. Chem. Commun. 433.
R. B. King (1994). Inorg. Chim. Acta 227, 207.
(a) T. H. Lemmen, L. C. Huffman, and K. G. Caulton (1986). Angew. Chem. Int. Ed. Engl. 25, 262. (b) P. A. Leach, S. J. Geib, and N. J. Cooper (1992). Organometallics 11, 4367. (c) F. Calderazzo, G. Pampaloni, U. Englert, and J. Strä hle (1990). J. Organomet. Chem. 383, 45. (d) F. Bachechi, J. Ott, and L. M. Venanzi (1985). J. Am. Chem. Soc. 107, 1760. (e) A Antinolo, J. K. Burdett, B. Chaudret, O. Eisenstein, M. Fajardo, F. Jalon, F. Lahoz, J. A. Lopex, and A. Otero (1990). J. Chem. Soc. Chem. Commun. 17.
A. E. Reed, L. A. Curtiss, and F. Weinhold (1988). Chem. Rev. 88, 899.
(a) R. Bouwman and W. M. H. Sachtler (1970). J. Catal. 19, 127. (b) R. Bouwman, G. J. M. Lippits, and W. M. H. Sachtler (1972). J. Catal. 25, 350. (c) F. L. Williams and M. Boudart (1973). J. Catal. 30, 438.
(a) J. C. Tracy (1972). J. Chem. Phys. 56, 2748. (b) J. C. Tracy (1972). J. Chem. Phys. 56, 2736. (c) K. Christmann, O. Schober, and J. G. Ertl (1974). J. Chem. Phys. 60, 4719. (d) K. Y. Yu, D. T. Ling, and W. E. Spicer (1976). J. Catal. 44, 373.
D. M. P. Mingos and L. Zhenyang (1989). Comments Inorg. Chem. 9, 95.
(a) D. A. Nagaki, Ph.D. thesis (University of Wisconsin, Madison, 1986). (b) D. A. Nagaki, L. D. Lower, G. Longoni, P. Chini, and L. F. Dahl (1986). Organometallics 5, 1764. (c) G. Longoni and P. Chini (1976). Inorg. Chem. 15, 3029.
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Mlynek, P.D., Kawano, M., Kozee, M.A. et al. First-Known High-Nuclearity Copper–Nickel Carbonyl Cluster: [CuxNi35−x(CO)40]5− (with x=3 or 5) Containing an Unprecedented 35-Atom Three-Layer hcp Triangular Stacking Metal-Core Geometry. Journal of Cluster Science 12, 313–338 (2001). https://doi.org/10.1023/A:1016699702233
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DOI: https://doi.org/10.1023/A:1016699702233