3. The use of a support as a ligand brings a supplementary electronic and steric
parameter.
4. The surface organometallic complexes are thermally much more stable than
their molecular counterpart. The example of [(Si–O) WMe 5 ] on silica which is
stable up to 100
C is a good example of the ability of a surface to stabilize a
molecular compound which is explosive at room temperature! So reactions can
be performed on organometallic compounds at very high temperature which is
not possible in classical homogeneous catalysis. Such stability allows the observation of carbynes, carbenes, alkyls, amido, imido, and hydrides even at elevated
temperatures.
The absence of bimolecular reactions avoids many deactivation processes and
allows better lifetime of the catalysts. This is a well-known concept but repetition is
a source of pedagogy.
Using a variety of single-site surface complexes bearing simultaneously several
types of highly reactive ligands has been at the origin of the various concepts of
single-site multifunctional catalysts:
• Monofunctional with metal hydride(s): (Ziegler–Natta depolymerization,
hydrogenolysis of waxes, olefin polymerization), metal carbenes (olefin metathesis, ROMP ADMET, etc.)
• Bifunctional with metal hydrides (or alkyls) (conversion of butenes to
propylene)
• Trifunctional (conversion of ethylene to propylene, metathesis of alkanes,
cycloalkanes, etc.)
References
1. Vidal V, Theolier A, Thivolle-Cazat J, Basset JM (1997) Science 276:99–102
2. Basset JM, Ugo R (2009) Modern surface organometallic chemistry. Wiley-VCH, Weinheim,
pp 1–21
3. Corker J, Lefebvre F, Lecuyer C, Dufaud V, Quignard F, Choplin A, Evans J, Basset JM
(1996) Science 271:966–969
4. Dufaud VR, Basset JM (1998) Angew Chem Int Ed 37:806–810
5. Goldman AS, Roy AH, Huang Z, Ahuja R, Schinski W, Brookhart M (2006) Science 312:
257–261
6. Huang Z, Rolfe E, Carson EC, Brookhart M, Goldman AS, El-Khalafy SH, MacArthur AHR
(2010) Adv Synth Catal 352:125–135
7. Herisson JL, Chauvin Y (1971) Makromol Chem 141:161–176
8. Schrock RR, Murdzek JS, Bazan GC, Robbins J, Dimare M, Oregan M (1990) J Am Chem Soc
112:3875–3886
9. Bazan GC, Oskam JH, Cho HN, Park LY, Schrock RR (1991) J Am Chem Soc 113:6899–6907
10. Schwab P, Grubbs RH, Ziller JW (1996) J Am Chem Soc 118:100–110
11. Nguyen ST, Grubbs RH, Ziller JW (1993) J Am Chem Soc 115:9858–9859
12. Ertl G (1983) J Vac Sci Technol A 1:1247–1253
13. Cariati E, Dragonetti C, Lucenti E, Roberto D, Ugo R (2009) Modern surface organometallic
chemistry. Wiley-VCH, Weinheim, pp 639–683
184
M.K. Samantaray et al.
parameter.
4. The surface organometallic complexes are thermally much more stable than
their molecular counterpart. The example of [(Si–O) WMe 5 ] on silica which is
stable up to 100
C is a good example of the ability of a surface to stabilize a
molecular compound which is explosive at room temperature! So reactions can
be performed on organometallic compounds at very high temperature which is
not possible in classical homogeneous catalysis. Such stability allows the observation of carbynes, carbenes, alkyls, amido, imido, and hydrides even at elevated
temperatures.
The absence of bimolecular reactions avoids many deactivation processes and
allows better lifetime of the catalysts. This is a well-known concept but repetition is
a source of pedagogy.
Using a variety of single-site surface complexes bearing simultaneously several
types of highly reactive ligands has been at the origin of the various concepts of
single-site multifunctional catalysts:
• Monofunctional with metal hydride(s): (Ziegler–Natta depolymerization,
hydrogenolysis of waxes, olefin polymerization), metal carbenes (olefin metathesis, ROMP ADMET, etc.)
• Bifunctional with metal hydrides (or alkyls) (conversion of butenes to
propylene)
• Trifunctional (conversion of ethylene to propylene, metathesis of alkanes,
cycloalkanes, etc.)
References
1. Vidal V, Theolier A, Thivolle-Cazat J, Basset JM (1997) Science 276:99–102
2. Basset JM, Ugo R (2009) Modern surface organometallic chemistry. Wiley-VCH, Weinheim,
pp 1–21
3. Corker J, Lefebvre F, Lecuyer C, Dufaud V, Quignard F, Choplin A, Evans J, Basset JM
(1996) Science 271:966–969
4. Dufaud VR, Basset JM (1998) Angew Chem Int Ed 37:806–810
5. Goldman AS, Roy AH, Huang Z, Ahuja R, Schinski W, Brookhart M (2006) Science 312:
257–261
6. Huang Z, Rolfe E, Carson EC, Brookhart M, Goldman AS, El-Khalafy SH, MacArthur AHR
(2010) Adv Synth Catal 352:125–135
7. Herisson JL, Chauvin Y (1971) Makromol Chem 141:161–176
8. Schrock RR, Murdzek JS, Bazan GC, Robbins J, Dimare M, Oregan M (1990) J Am Chem Soc
112:3875–3886
9. Bazan GC, Oskam JH, Cho HN, Park LY, Schrock RR (1991) J Am Chem Soc 113:6899–6907
10. Schwab P, Grubbs RH, Ziller JW (1996) J Am Chem Soc 118:100–110
11. Nguyen ST, Grubbs RH, Ziller JW (1993) J Am Chem Soc 115:9858–9859
12. Ertl G (1983) J Vac Sci Technol A 1:1247–1253
13. Cariati E, Dragonetti C, Lucenti E, Roberto D, Ugo R (2009) Modern surface organometallic
chemistry. Wiley-VCH, Weinheim, pp 639–683
184
M.K. Samantaray et al.