in accelerating the reaction is not always clear. The potential for the second metal to
coordinate other functional groups within the substrate and thereby provide a
favourable structural or electronic influence on the reaction has been postulated.
Equally important is the steric environment created by the bimetallic structure,
especially where an enhancement of the reaction selectivity is observed.
No matter what function the bimetallic catalyst fulfils, two key trends of catalyst
design emerge from the above examples: (1) a relatively constrained catalyst
structure is often essential to ensure a beneficial interaction of both metals; this
most likely helps overcome the entropic penalty associated with creating an ordered
bimetallic transition state during the catalytic cycle; (2) for catalysts that do not
contain any prearranged metal–metal bonding or bridging atom interactions, a
relatively short intermetallic distance also appears necessary. Clearly, for many
of the catalysts described here, much work remains to understand exactly how the
bimetallic structure enhances the catalysts performance.
References
1. Wilcox DE (1996) Chem Rev 96:2435. doi:10.1021/cr950043b
2. van den Beuken EK, Feringa BL (1998) Tetrahedron 54:12985. doi:10.1016/S0040-4020(98)
00319-6
3. Gavrilova AL, Bosnich B (2004) Chem Rev 104:349. doi:10.1021/cr020604g
4. Shibasaki M, Matsunaga S (2006) Chem Soc Rev 35:269. doi:10.1039/B506346A
5. Delferro M, Marks TJ (2011) Chem Rev 111:2450. doi:10.1021/cr1003634
6. Park J, Hong S (2012) Chem Soc Rev 41:6931. doi:10.1039/C2CS35129C
7. Bratko I, Gomez M (2013) Dalton Trans 42:10664. doi:10.1039/C3DT50963J
8. Hashmi AS (2003) Gold Bull 36:3. doi:10.1007/BF03214859
9. Beller M, Seayad J, Tillack A, Jiao H (2004) Angew Chem Int Ed 43:3368. doi:10.1002/anie.
200300616
10. Omae I (2008) Appl Organomet Chem 22:149. doi:10.1002/aoc.1367
11. Chinchilla R, Na ´jera C (2013) Chem Rev 114:1783. doi:10.1021/cr400133p
12. Gervasio G, Sappa E, Secco A (2014) J Organomet Chem 751:111. doi:10.1016/j.
jorganchem.2013.08.046
13. Galan BR, Rovis T (2009) Angew Chem Int Ed 48:2830. doi:10.1002/anie.200804651
14. Chopade PR, Louie J (2006) Adv Synth Catal 348:2307. doi:10.1002/adsc.200600325
15. Schore NE (1988) Chem Rev 88:1081. doi:10.1021/cr00089a006
16. Matsuura M, Fujihara T, Kakeya M, Sugaya T, Nagasawa A (2013) J Organomet Chem
745–746:288. doi:10.1016/j.jorganchem.2013.07.035
17. Bonifaci C, Ceccon A, Gambaro A, Ganis P, Mantovani L, Santi S, Venzo A (1994)
J Organomet Chem 475:267. doi:10.1016/0022-328X(94)84031-8
18. Yan H, Beatty AM, Fehlner TP (2002) Organometallics 21:5029. doi:10.1021/om0205694
19. Yan H, Beatty AM, Fehlner TP (2001) Angew Chem Int Ed 40:4498. doi:10.1002/1521-3773
(20011203)40:23<4498::AID-ANIE4498>3.0.CO;2-3
20. Ohshita J, Furumori K, Matsuguchi A, Ishikawa M (1990) J Org Chem 55:3277. doi:10.1021/
jo00297a054
21. Trost BM, Kottirsch G (1990) J Am Chem Soc 112:2816. doi:10.1021/ja00163a062
22. Hidai M, Mizobe Y (2005) Can J Chem 83:358. doi:10.1139/v05-016
23. Qu ¨ J-P, Masui D, Ishii Y, Hidai M (1998) Chem Lett 27:1003. doi:10.1246/cl.1998.1003
134
M.J. Page et al.
coordinate other functional groups within the substrate and thereby provide a
favourable structural or electronic influence on the reaction has been postulated.
Equally important is the steric environment created by the bimetallic structure,
especially where an enhancement of the reaction selectivity is observed.
No matter what function the bimetallic catalyst fulfils, two key trends of catalyst
design emerge from the above examples: (1) a relatively constrained catalyst
structure is often essential to ensure a beneficial interaction of both metals; this
most likely helps overcome the entropic penalty associated with creating an ordered
bimetallic transition state during the catalytic cycle; (2) for catalysts that do not
contain any prearranged metal–metal bonding or bridging atom interactions, a
relatively short intermetallic distance also appears necessary. Clearly, for many
of the catalysts described here, much work remains to understand exactly how the
bimetallic structure enhances the catalysts performance.
References
1. Wilcox DE (1996) Chem Rev 96:2435. doi:10.1021/cr950043b
2. van den Beuken EK, Feringa BL (1998) Tetrahedron 54:12985. doi:10.1016/S0040-4020(98)
00319-6
3. Gavrilova AL, Bosnich B (2004) Chem Rev 104:349. doi:10.1021/cr020604g
4. Shibasaki M, Matsunaga S (2006) Chem Soc Rev 35:269. doi:10.1039/B506346A
5. Delferro M, Marks TJ (2011) Chem Rev 111:2450. doi:10.1021/cr1003634
6. Park J, Hong S (2012) Chem Soc Rev 41:6931. doi:10.1039/C2CS35129C
7. Bratko I, Gomez M (2013) Dalton Trans 42:10664. doi:10.1039/C3DT50963J
8. Hashmi AS (2003) Gold Bull 36:3. doi:10.1007/BF03214859
9. Beller M, Seayad J, Tillack A, Jiao H (2004) Angew Chem Int Ed 43:3368. doi:10.1002/anie.
200300616
10. Omae I (2008) Appl Organomet Chem 22:149. doi:10.1002/aoc.1367
11. Chinchilla R, Na ´jera C (2013) Chem Rev 114:1783. doi:10.1021/cr400133p
12. Gervasio G, Sappa E, Secco A (2014) J Organomet Chem 751:111. doi:10.1016/j.
jorganchem.2013.08.046
13. Galan BR, Rovis T (2009) Angew Chem Int Ed 48:2830. doi:10.1002/anie.200804651
14. Chopade PR, Louie J (2006) Adv Synth Catal 348:2307. doi:10.1002/adsc.200600325
15. Schore NE (1988) Chem Rev 88:1081. doi:10.1021/cr00089a006
16. Matsuura M, Fujihara T, Kakeya M, Sugaya T, Nagasawa A (2013) J Organomet Chem
745–746:288. doi:10.1016/j.jorganchem.2013.07.035
17. Bonifaci C, Ceccon A, Gambaro A, Ganis P, Mantovani L, Santi S, Venzo A (1994)
J Organomet Chem 475:267. doi:10.1016/0022-328X(94)84031-8
18. Yan H, Beatty AM, Fehlner TP (2002) Organometallics 21:5029. doi:10.1021/om0205694
19. Yan H, Beatty AM, Fehlner TP (2001) Angew Chem Int Ed 40:4498. doi:10.1002/1521-3773
(20011203)40:23<4498::AID-ANIE4498>3.0.CO;2-3
20. Ohshita J, Furumori K, Matsuguchi A, Ishikawa M (1990) J Org Chem 55:3277. doi:10.1021/
jo00297a054
21. Trost BM, Kottirsch G (1990) J Am Chem Soc 112:2816. doi:10.1021/ja00163a062
22. Hidai M, Mizobe Y (2005) Can J Chem 83:358. doi:10.1139/v05-016
23. Qu ¨ J-P, Masui D, Ishii Y, Hidai M (1998) Chem Lett 27:1003. doi:10.1246/cl.1998.1003
134
M.J. Page et al.