, Electronic Supplementary Information (ESI) available: Cartesian coordinates and free Gibbs energy for all the intermediates

J. Fiksel, Design for Environment: Creating Eco-Efficient Products ans Processes, 1998.

P. T. Anastas, L. Heine, and T. C. Williamson, Environ. Sci. Technol, vol.37, issue.5, pp.95-101, 2000.

R. K. Iler and R. K. , The Chemistry of Silica, vol.2, 1979.

. Wiley, . ;. Inc, and . Davydov, In Adsorption on Silica Surfaces, 1998.

E. Papirer, , vol.90, 2000.

M. Costa, J. Sodupe, P. Lambert, and . Ugliengo, Chem. Rev, vol.113, pp.4216-4313, 2013.

J. Basset, R. Psaro, D. Roberto, and R. Ugo, Modern Surface Organometallic Chemistry, 2009.

P. Sautet and F. Delbecq, Chem. Rev, vol.110, pp.1788-1806, 2010.

T. J. Woodman, Y. Sarazin, G. Fink, K. Hauschild, M. ;. Bochmann et al., J. Mol. Catal. A: Chem, vol.38, p.31, 1146.

C. Hamaide, R. Boisson, ;. Spitz, R. Gerstberger, and . Anwander, Microporous Mesoporous Mater, vol.202, issue.303, pp.44-45, 2001.

C. Gerstberger, R. Palm, . ;. Anwander, L. Gauvin, and R. Delevoye, Chem. Eur. J, vol.5, p.997, 1999.

A. Hassan, J. Keldenich, and A. Mortreux, Inorg. Chem, vol.46, 1062.

R. Storz and . Anwander, J. Am. Chem. Soc, p.16368, 2010.

R. Anwander and R. Roesky, J. Chem. Soc, pp.137-138, 1997.

E. Le-roux and R. Anwander, Surface Organolanthanide and Actinide Chemistry

-. Wiley, &. Gmbh, . Co, and . Kgaa, , 2009.

R. Anwander, O. Runte, J. Eppinger, G. Gestberger, H. Herdtweck et al., J. Chem. Soc, vol.5, pp.847-858, 1998.

L. T. Zhuravlev, Colloids Surf., A, vol.173, issue.1, 1987.

J. W. Trebosc, S. Wiench, V. S. Huh, M. J. Lin, and . Pruski, J. Am. Chem. Soc, vol.127, p.3057, 2005.

J. P. Burneau and . Gallas, The Surface Properties of Silicas

A. P. Legrand,

. Chichester, High Resolution Solid State NMR of Silicates and Zeolites, pp.145-234, 1998.

;. R. Wiley-&-sons, H. W. Anwander, G. Görlitzer, C. Gerstberger, . Palm et al., J. Chem. Soc, vol.10, 1987.

). K. Tortosa, T. Hamaide, C. Boisson, and R. Splitz, Dalton Trans, pp.3611-3615, 1999.

). R. Anwander, Chem. Mater, vol.202, pp.4419-4438, 2001.

Y. Chen, Z. Zhy, J. Zhang, J. Shen, and X. Zhou, J. Organomet. Chem, pp.3873-3789, 2005.

I. Del-rosal, I. C. Gerber, R. Poteau, and L. Maron, J. Phys. Chem. A, vol.114, pp.6322-6330, 2010.

X. Rozanska, F. Delbecq, and P. Sautet, Phys ; Chem. Chem. Phys, vol.12, pp.14930-149140, 2010.

J. Sauer, P. Ugliengo, E. Garrone, and V. R. Saunders, Chem. Rev, vol.94, 1994.

C. Zwijnenburg, T. J. Van-alsenoy, and . Maschmeyer, Phys. Chem. A, vol.106, pp.12376-12385, 2002.

M. Antonietti, U. Michalski, H. Heiz, K. H. Jones, N. Lim et al., Phys. ReV. Lett, vol.94, p.213402, 2005.

F. Copéret, J. Lefebvre, X. Basset, O. Solans-monfort, W. W. Eisenstein et al., Organometallics, vol.25, pp.3554-3557, 2006.

A. Copéret, Z. J. Sinha, R. R. Tonzetich, X. Schrock, E. Solans-monfort et al.,

L. J. Lesage, ). B. Emsley-;-f, E. Civalleri, P. Garrone, and . Ugliengo, J. Am. Chem. Soc, vol.130, pp.443-450, 1999.

F. Vignemaeder and P. Sautet, J. Phys. Chem. B, vol.101, pp.8197-8203, 1997.

. Ugliengo, J. Phys. Chem. B, vol.104, p.9491, 2000.

. Tuttle, Nucler. Inst. Met. Phys. Res. B, vol.250, pp.274-278, 2006.

A. Catlow, W. Brown, A. ;. Goumans, and C. R. , Mon. Not. R. Astron. Soc, vol.382, 1829.

W. A. Catlow, ;. Brown, M. Ugliengo, F. Sodupe, I. J. Musso et al., J. Chem. Phys, vol.128, p.4579, 2008.

F. Lambert, D. Mauri, and . Costa, Chem. Mater, p.3336, 1920.

X. Solans-monfort, J. Filhol, C. Copéret, and O. Eisenstein, New. J. Chem, vol.30, pp.842-850, 2006.

M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb et al.,

J. Montgomery, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam et al.,

B. Barone, M. Mennucci, G. Cossi, N. Scalmani, G. A. Rega et al.,

K. Ehara, R. Toyota, J. Fukuda, M. Hasegawa, T. Ishida et al.,

M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross et al.,

R. E. Gomperts, O. Stratmann, A. J. Yazyev, R. Austin, C. Cammi et al.,

K. Ayala, G. A. Morokuma, P. Voth, J. J. Salvador, and . Dannenberg,

V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas et al.,

G. Stefanov, A. Liu, P. Liashenko, I. Piskorz, R. L. Komaromi et al.,

C. Y. Al-laham, A. Peng, M. Nanayakkara, P. M. Challacombe, B. Gill et al.,

W. Wong, C. Gonzalez, J. A. Pople, and . Perdew, Unified Theory of Exchange and Correlation Beyond the Local Density Approximation, In Electronic Structure of Solids, vol.17, 2003.

). J. Perdew, K. Burke, and Y. Wang, Akademie: Berlin, vol.54, 1991.

P. Perdew and Y. Wang, Derivation of a Generalized Gradient Approximation: The PW91 Density Functional, Electronic Density Functional Theory: Recent Progress and New Directions

J. ,

G. Dobson, M. P. Vignale, and . Mas, , 1998.

H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, C. P. Fiolhais-;-e)-j et al., Phys. Rev. B, vol.46, pp.6671-6687, 1992.

J. A. Perdew, S. H. Chevary, K. A. Vosko, M. R. Jackson, D. J. Pederson et al., Phys. Rev. B, vol.48, pp.4978-4978, 1993.

M. Dolg, H. Stoll, and H. J. Preuss, J. Mol. Struct.:THEOCHEM, vol.90, pp.139-147, 1730.

P. C. Hariharan and J. A. Pople, Theor. Chim. Acta, vol.28, 1972.

F. J. London-;-b)-r.-mcweeny-;-c)-r.-ditchfield-;-d)-j, R. Dodds, A. Mcweeny, and J. Sadlej, J. Phys. Radium, vol.8, pp.1779-1791, 1937.

H. Staub, I. Del-rosal, L. Maron, F. Kleitz, F. Fontaine-;-b et al., J. Am. Chem. Soc, vol.116, pp.9263-9275, 2012.

N. Merle, G. Girard, N. Popoff, A. De-mallmann, Y. Bouhoute et al., Inorg. Chem, vol.52, pp.4232-4241, 2013.

I. Boisson, L. Del-rosal, A. Maron, R. M. De-mallmann, M. Gauvin et al., Chem. Eur. J, vol.19, pp.964-973, 2013.

A. E. Reed and F. J. Weinhold, Chem. Phys, vol.78, pp.899-926, 1983.

O. W. Flörke, H. A. Graetsch, F. Brunk, L. Benda, S. Paschen et al.,

C. Welsh, M. Libanati, D. Ettlinger, M. Kerner, W. Maier et al., Ullmann's Encyclopedia of Industrial Chemistry, 2008.

V. D. Khavryuchenko, O. V. Khavryuchenko, and V. V. Lisnyak, Critical Reviews in Solid State and Materials Sciences, vol.36, pp.47-65, 2011.

D. Barby, . K. Silicas-;-b)-r, and . Iler, The Chemistry of Silica, « Characterization of Powder Surfaces, p.353, 1976.

E. Fink, J. ;. Bohm, M. Buckley, and . Greenblatt, Coll. Interface Sci, vol.26, pp.599-602, 1968.

, Adsorption on Silica Surfaces

E. J. Papirer-;-b, ). J. Humbert-;-b, P. Gnado, and C. Dhamelincourt, Non-Cryst. Solids, vol.90, pp.29-37, 1995.

M. Pélégris, A. L. Traisnel, and . Mayot, Non-Cryst.Solids, vol.208, pp.247-258, 1996.

J. Czuryszkiekiewicz, P. Ahvenlammi, M. Kortesuo, F. Ahola, M. Kleitz et al., J. Non-Cryst. Solids, vol.306, pp.1-10, 2002.

A. P. Legrand, H. Hommel, A. Tuel, A. Vidal, H. Balard et al.,

R. Czernichowski, H. V. Erre, and . Damme, AdV. Colloid Interface Sci, vol.33, pp.91-330, 1990.

H. K. Mueller, K. Kammler, S. E. Wegner, and . Pratsinis, Langmuir, vol.19, pp.160-165, 2003.

K. Fischer-;-b, ). H. Gilman, L. S. Miller, and J. , Angew. Chem., Int. Ed. Eng, vol.26, pp.394-396, 1935.

). F. Brown-;-c, A. J. Armistead, F. H. Tyler, S. A. Hambleton, J. A. Mitchell et al., J. Polym. Sci., Part A, vol.73, pp.437-453, 1951.

A. Bolis, A. B. Cavenago, ;. Fubini, B. Bolis, and L. Fubini, Langmuir, vol.13, p.895, 1997.

G. Marchese, D. J. Martra, and . Costa, Chem. Soc., Faraday Trans, vol.87, pp.7141-7145, 1987.

P. V. Voort, E. F. Vansant-;-c)-x, G. Q. Zhao, and . Lu, J. Phys. Chem. B, vol.71, pp.1556-1561, 1997.

E. J. Cho, F. V. Bright, and F. V. , Anal. Chem, vol.73, p.3289, 2001.

L. Maron, L. Perrin, and O. Eisenstein, J. Chem. Soc, vol.34, pp.4355-4362, 2002.

L. Maron and O. Eisenstein, New J. Chem, pp.255-258, 2001.

G. Lapadula, A. Bourdolle, F. Allouche, M. P. Conley, I. Del-rosal et al.,

C. Guyot, S. Andraud, C. Brasselet, O. Copéret, R. A. Maury et al., Chem. Mater, vol.26, pp.1062-1073, 2014.

D. C. Bradley and Y. C. Gao-polyhedron, , vol.1, pp.307-310, 1982.

J. Smith, Chem. Soc. Dalton Trans, pp.153-156, 1992.

J. P. Osegovic and R. S. Drago, Journal of Catalysis, vol.182, pp.1-4, 1999.

, Drago J. Phys. Chem. B, vol.104, pp.147-154, 2000.