N,N-Dialkylcarbamato complexes as precursors for the chemical implantation of metal cations on a silica support. Part 3 Palladium

Abstract

Chemical implantation of palladium(II) has been carried out under mild conditions by reacting trans-Pd(O₂CNEt₂)₂(NHEt₂)₂ with the silanol groups of amorphous silica, carbon dioxide and secondary amine being released in the process. The palladium-containing silica has been characterized and the coordination environment of the implanted cation has been defined by ¹³C CP MAS NMR, DRIFT and XPS spectra, and by WAXS measurements. Silica-bonded palladium(II) was reduced thermally in vacuo or with dihydrogen at room temperature. Catalytic activity in the hydrogenation of cyclohexene was found for all samples containing the silica-supported reduced palladium; the best results, with rates independent of olefin concentration, were found for the samples treated thermally (200°C) under reduced pressure.

References

1. (a) L. Abis, D. Belli Dell' Amico, F. Calderazzo, R. Caminiti, F. Garbassi, S. Ianelli, G. Pelizzi, P. Robino and A. Tomei, J. Mol. Catal., 1996, 108, L113; (b) L. Abis, D. Belli Dell' Amico, C. Busetto, F. Calderazzo, R. Caminiti, C. Ciofi, F. Garbassi and G. Masciarelli, J. Mater. Chem., 1998, 8, 751.
2. (a) J. M. Tour, S. L. Pendalwar and J. P. Cooper, Chem. Mater., 1990, 2, 647; (b) B. Breitscheidel, J. Zieder and U. Schubert, Chem. Mater., 1991, 3, 559; (c) J. A. Schwarz, C. Contescu and A. Contescu, Chem. Rev., 1995, 95, 477; (d) K. Okitsu, H. Bandow, Y. Maeda and Y. Nagata, Chem. Mater., 1996, 8, 315.
3. D. G. H. Ballard, Adv. Catal., 1973, 23, 267; Yu. I. Yermakov and V. Zakharov, Adv. Catal., 1975, 24, 173; H. C. Foley, S. J. DeCanio, K. D. Tau, K. J. Chao, J. H. Onuferko, C. Dybowski and B. C. Gates, J. Am. Chem. Soc., 1983, 105, 3074; J. Schwartz, Acc. Chem. Res., 1985, 18, 302; Y. Iwasawa, Inorganic Oxide-attached Metal Catalysts, in, Tailored Metal Catalysts, ed. Y. Iwasawa and D. Reidel Publ. Co., Dordrecht, 1986; S. A. Vierkötter, C. E. Barnes, T. L. Hatmaker, J. E. Penner-Hahn, C. M. Stinson, B. A. Huggins, A. Benesi and P. D. Ellis, Organometallics, 1991, 10, 3803; T. J. Marks, Acc. Chem. Res., 1992, 25, 57; S. L. Scott, P. Dufour, C. C. Santini and J.-M. Basset, Inorg. Chem., 1996, 35, 869; V. Vidal, A. Théolier, J. Thivolle-Cazat and J.-M. Basset, Science, 1997, 276, 99.
4. A. Anillo, D. Belli Dell' Amico, F. Calderazzo, M. Nardelli, G. Pelizzi and L. Rocchi, J. Chem. Soc., Dalton Trans., 1991, 2845.
5. Handbook of Chemistry and Physics, ed. D. R. Lide, CRC Press, Boca Raton–Ann Arbor, London–Tokyo, 75th edn., 1994–1995, p. 8–21.
6. (a) Z. Karpinski, Adv. Catal., 1990, 37, 45; (b) Z. Zhang, F. A. P. Cavalcanti and W. M. H. Sachtler, Catal. Lett., 1992, 12, 157; (c) A. Renou and M. Gillet, Surf. Sci., 1981, 106, 27; (d) F. C. Meldrum, N. A. Kotov and J. H. Fendler, Chem. Mater., 1995, 7, 1112; (e) J.-C. Hierso, C. Satto, R. Feurer and P. Kalck, Chem. Mater., 1996, 8, 2481; (f) G. Schmid, M. Harms, J.-O. Malm, J.-O. Bovin, J. van Ruitenbeck, H. W. Zandbergen and W. T. Fu, J. Am. Chem. Soc., 1993, 115, 2046; (g) W. Lin, T. H. Warren, R. G. Nuzzo and G. S. Girolami, J. Am. Chem. Soc., 1993, 115, 11644; (h) Yu. I. Yermakov, B. N. Kuznetsov and V. A. Zakharov, Catalysis by Supported Complexes, Elsevier, Amsterdam, 1981, ch. 2; A. Zecchina and C. Otero Areán, Catal. Rev.—Sci. Eng., 1993, 35, 261; W. Lin, B. C. Wiegand, R. G. Nuzzo and G. S. Girolami, J. Am. Chem. Soc., 1996, 118, 5977; W. Lin, R. G. Nuzzo and G. S. Girolami, J. Am. Chem. Soc., 1996, 118, 5988.
7. F. Calderazzo and F. A. Cotton, Inorg. Chem., 1962, 1, 30.
8. (a) J. F. Moulder, W. F. Stickle, P. E. Sobol and K. D. Bomben, Handbook of X-ray Photoelectron Spectroscopy, ed. J. Chastain, Perkin–Elmer Corporation, Eden Prairie, MN, 1994; (b) K. S. Kim, A. F. Gossmann and N. Winograd, Anal. Chem., 1974, 46, 197; (c) Y. Takasu, R. Unwin, B. Tesche, A. M. Bradshaw and M. Grunze, Surf. Sci., 1978, 77, 219; (d) G. L. Haller and D. E. Resasco, Adv. Catal., 1989, 36, 173.
9. (a) R. Caminiti, C. Sadun, V. Rossi, F. Cilloco and R. Felici, 25th Italian Congress of Physical Chemistry, Cagliari, Italy, June 17–21, 1991; Ital. Pat., 01261484, June 23rd 1993; (b) M. Carbone, R. Caminiti and C. Sadun, J. Mater. Chem., 1996, 6, 1709.
10. (a) R. Caminiti, R. Cucca and T. Radnai, J. Phys. Chem., 1984, 88, 2382; (b) G. Paschina, G. Piccaluga and M. Magini, J. Chem. Phys., 1984, 81, 6201; (c) R. Caminiti, D. Atzei, P. Cucca, A. Anedda and G. Bongiovanni, J. Phys. Chem., 1986, 90, 238; (d) R. Caminiti, C. Sadun, M. Basanisi and M. Carbone, J. Mol. Liq., 1996, 20, 55.
11. (a) R. Caminiti, C. Munoz Roca, D. Beltran-Porter and A. Z. Rossi, Z. Naturforsch., Teil A, 1988, 43, 591; (b) A. Musinu, G. Piccaluga and G. Pinna, J. Non-Cryst. Solids, 1990, 122, 52; (c) A. Capobianchi, A. M. Paoletti, G. Pennesi, G. Rossi, R. Caminiti and C. Ercolani, Inorg. Chem., 1994, 33, 4635; (d) D. Atzei, R. Caminiti, C. Sadun, R. Bucci and A. Corrias, Phosphorus Sulfur Silicon, 1993, 79, 13.
12. (a) W. Bol, G. J. H. Gerrit and C. van Panthaleon, J. Appl. Crystallogr., 1970, 3, 486; (b) G. Johansson and R. Caminiti, Z. Naturforsch., Teil A, 1986, 41, 1325; (c) R. Caminiti, F. Cilloco and R. Felici, Mol. Phys., 1992, 76, 681.
13. R. W. James, The Optical Principles of the Diffraction of X-rays, G. Bell & Sons Ltd, London, 1950.
14. (a) M. J. Auburn, R. D. Holmes-Smith, S. R. Stobart, M. J. Zaworotko, T. S. Cameron and A. Kumari, J. Chem. Soc., Chem. Commun., 1983, 1523; (b) P. Braunstein, M. Knorr, A. Tiripicchio and M. Tiripicchio Camellini, Angew. Chem., Int. Ed. Engl., 1989, 28, 1361; (c) T. A. Budzichowski, S. T. Chacon, M. H. Chisholm, F. J. Feher and W. Streib, J. Am. Chem. Soc., 1991, 113, 689; (d) M. Huang and C. W. DeKock, Inorg. Chem., 1993, 32, 2287; (e) A. Vizi-Orosz, R. Ugo, R. Psaro, A. Sironi, M. Moret, C. Zucchi, F. Ghelfi and G. Pályi, Inorg. Chem., 1994, 33, 4600; (f) M. Knorr, P. Braunstein, A. Tiripicchio and F. Ugozzoli, Organometallics, 1995, 14, 4910; (g) K. Su, T. Don Tilley and M. J. Sailor, J. Am. Chem. Soc., 1996, 118, 3459; (h) K. W. Terry, C. G. Lugmair, P. K. Gantzel and T. Don Tilley, Chem. Mater., 1996, 8, 274.
15. O. Glatter and O. Kratky, Small Angle X-ray Scattering, Academic Press, London, 1982.
16. (a) W. Palczewska, Adv. Catal., 1975, 24, 245; (b) J. J. S. Scholten and J. A. Konvalinka, J. Catal., 1966, 5, 1; (c) H. W. King and F. D. Manchester, Phys. Status Solidi, 1971, 45, 527; (d) Y. P. Khodyrev, R. V. Baranova, R. M. Imamov and S. A. Semiletov, Kristallofiya, 1978, 23, 1046; (e) Y. P. Khodyrev, R. V. Baranova, R. M. Imamov and S. A. Semiletov, Izv. Akad. Nauk SSSR, Neorg. Mater., 1978, 14, 1645; (f) S. A. Semiletov, R. V. Baranova, Yu. P. Khodyrev and R. M. Imamov, Kristallofiya, 1980, 25, 1162; (g) R. V. Baranova, Yu. P. Khodyrev, R. M. Imamov and S. A. Semiletov, Kristallofiya, 1980, 25, 1290; (h) P. Chou and M. A. Vannice, J. Catal., 1987, 104, 1; (i) C. H. Foo, C. T. Hong and C.-T. Yeh, J. Chem. Soc., Faraday Trans., 1989, 85, 65; (j) S.-C. Chou, S.-H. Lin and C.-T. Yeh, J. Chem. Soc., Faraday Trans., 1995, 91, 949 and references therein; (k) Y. Sakamoto, M. Imoto, K. Takai, T. Yanaru and K. Ohshima, J. Phys.: Condens. Matter, 1996, 8, 3229.
17. (a) JCPDS, Joint Committee on Powder Diffraction Standards, 1601 Park Lane, Swarthmore, PA, Card No. 5–0681; (b) H. E. Swanson and E. Tatge, NBS Circular No. 539, 1953, vol. 1, p. 21; (c) J. Donohue, The Structure of the Elements, J. Wiley, New York, 1974; (d) K. L. Shelton, P. A. Merewether and B. J. Skinner, Can. Mineral., 1981, 19, 599.
18. (a) J. Horiuti and M. Polanyi, Trans. Faraday Soc., 1934, 30, 1164; (b) E. E. Gonzo and M. Boudart, J. Catal., 1978, 52, 462; (c) G. Leclercq and M. Boudart, J. Catal., 1981, 71, 127; (d) N. Koga, C. Daniel, J. Han and K. Morokuma, J. Am. Chem. Soc., 1987, 109, 3455; (e) L. Çerveny and V. Ruzicka, Adv. Catal., 1981, 30, 335; (f) G. C. Bond, Surf. Sci., 1985, 156, 966; (g) M. Boudart and D. J. Sajkowski, Faraday Discuss., 1991, 92, 57; (h) M. Boudart and K. Tamaru, Catal. Lett., 1991, 9, 15; (i) J. Barbier, F. Lamy-Pitara, P. Marecot, J. P. Boitiaux, J. Cosyns and F. Verna, Adv. Catal., 1990, 37, 279; (j) H. Arnold, S. Göbel, D. Reinig and J. Gaube, Chem. Ing. Tech., 1994, 66, 727.
19. (a) M. Boudart and D. J. Sajkowski, J. Chem. Soc., Faraday Discuss., 1991, 92, 57; (b) M. Che and C. O. Bennett, Adv. Catal., 1989, 36, 55.
20. M. Boudart, Chem. Rev., 1995, 95, 661.