bond. The paddlewheel [Ru 2 (CO) 4 ]
2+ core is an ideal platform for axial reactivity.
A variety of bridging ligands are incorporated at equatorial sites on the
[Ru 2 (CO) 4 ]
2+ core to tune the reactivity and selectivity keeping the axial sites
available for reactions. Bera et al. have studied stoichiometric reactions such as
C–H activation and C–C bond formation at sites trans to the [Ru–Ru] single bond.
Mass et al. have explored catalytic cyclopropanation and C–H insertion via
carbene-transfer reactions. Introduction of NHC unit in the ligand skeleton
increases the catalytic efficiency. Gois et al. have demonstrated that multiply
bonded diruthenium compounds are excellent catalysts for catalytic C–H
amination. Berry et al. reported electron delocalization on [Ru–Ru]N system
that makes the N atom highly electrophilic. Metal–metal bonded [Ru–Ru] complexes are beginning to show promise as organometallic catalysts. Further work is
needed to realize the full potential of these complexes.
Acknowledgments This work is financially supported by the Department of Science and Technology (DST), India, and the Council of Scientific and Industrial Research (CSIR) of India. J.K.B.
thanks Department of Atomic Energy for DAE outstanding investigator award. I.D. thanks CSIR,
India, and G.S. thanks IIT Kanpur for fellowships.
References
1. Cotton FA, Walton RA (eds) (1982) Multiple bonds between metal atoms, 1st edn. Wiley,
New York
2. Cotton FA, Walton RA (eds) (1993) Multiple bonds between metal atoms, 2nd edn.
Oxford University Press, New York
3. Chisholm MH (2007) Proc Natl Acad Sci 104:2563
4. Parkin G (ed) (2010) Metal-metal bonding. Springer, Heidelberg/Berlin
5. Kepert DL, Vrieze K (eds) (1973) Compounds of the transition elements involving metalmetal bonds, vol 27, 1st edn, Pergamon texts in inorganic chemistry. Pergamon, Oxford
6. Cotton FA, Walton RA (eds) (2005) Multiple bonds between metal atoms, 3rd edn. Springer,
New York
7. Liddle ST (ed) (2015) Molecular metal-metal bonds: compounds, synthesis, properties .
Wiley, Weinheim
8. Lippard SJ, Chisholm MH, Rothwell IP (eds) (2007) Chemical reactions of metal-metal
bonded compounds of the transition elements, progress in inorganic chemistry, vol 29. Wiley,
New York
9. Shibasaki M, Yamamoto Y (eds) (2004) Multimetallic catalysis in organic synthesis.
Wiley, Weinheim
10. Li C, Widjaja E, Garland M (2003) J Am Chem Soc 125:5540
11. Broussard ME, Juma B, Train SG, Peng W-J, Laneman SA, Stanley GG (1993)
Science 260:1784
12. Adams RD, Cotton FA (1998) Bimetallic homogeneous hydroformylation. In: Adams RD,
Cotton FA (eds) Catalysis by di- and polynuclear metal complexes. Wiley, New York,
pp 345–372
13. Parka J, Hong S (2012) Chem Soc Rev 41:6931
14. Matsunaga S, Shibasaki M (2014) Chem Commun 50:1044
15. Esswein AJ, Veige AS, Nocera DG (2005) J Am Chem Soc 127:16641
16. Gray TG, Veige AS, Nocera DG (2004) J Am Chem Soc 126:9760
Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond
95
2+ core is an ideal platform for axial reactivity.
A variety of bridging ligands are incorporated at equatorial sites on the
[Ru 2 (CO) 4 ]
2+ core to tune the reactivity and selectivity keeping the axial sites
available for reactions. Bera et al. have studied stoichiometric reactions such as
C–H activation and C–C bond formation at sites trans to the [Ru–Ru] single bond.
Mass et al. have explored catalytic cyclopropanation and C–H insertion via
carbene-transfer reactions. Introduction of NHC unit in the ligand skeleton
increases the catalytic efficiency. Gois et al. have demonstrated that multiply
bonded diruthenium compounds are excellent catalysts for catalytic C–H
amination. Berry et al. reported electron delocalization on [Ru–Ru]N system
that makes the N atom highly electrophilic. Metal–metal bonded [Ru–Ru] complexes are beginning to show promise as organometallic catalysts. Further work is
needed to realize the full potential of these complexes.
Acknowledgments This work is financially supported by the Department of Science and Technology (DST), India, and the Council of Scientific and Industrial Research (CSIR) of India. J.K.B.
thanks Department of Atomic Energy for DAE outstanding investigator award. I.D. thanks CSIR,
India, and G.S. thanks IIT Kanpur for fellowships.
References
1. Cotton FA, Walton RA (eds) (1982) Multiple bonds between metal atoms, 1st edn. Wiley,
New York
2. Cotton FA, Walton RA (eds) (1993) Multiple bonds between metal atoms, 2nd edn.
Oxford University Press, New York
3. Chisholm MH (2007) Proc Natl Acad Sci 104:2563
4. Parkin G (ed) (2010) Metal-metal bonding. Springer, Heidelberg/Berlin
5. Kepert DL, Vrieze K (eds) (1973) Compounds of the transition elements involving metalmetal bonds, vol 27, 1st edn, Pergamon texts in inorganic chemistry. Pergamon, Oxford
6. Cotton FA, Walton RA (eds) (2005) Multiple bonds between metal atoms, 3rd edn. Springer,
New York
7. Liddle ST (ed) (2015) Molecular metal-metal bonds: compounds, synthesis, properties .
Wiley, Weinheim
8. Lippard SJ, Chisholm MH, Rothwell IP (eds) (2007) Chemical reactions of metal-metal
bonded compounds of the transition elements, progress in inorganic chemistry, vol 29. Wiley,
New York
9. Shibasaki M, Yamamoto Y (eds) (2004) Multimetallic catalysis in organic synthesis.
Wiley, Weinheim
10. Li C, Widjaja E, Garland M (2003) J Am Chem Soc 125:5540
11. Broussard ME, Juma B, Train SG, Peng W-J, Laneman SA, Stanley GG (1993)
Science 260:1784
12. Adams RD, Cotton FA (1998) Bimetallic homogeneous hydroformylation. In: Adams RD,
Cotton FA (eds) Catalysis by di- and polynuclear metal complexes. Wiley, New York,
pp 345–372
13. Parka J, Hong S (2012) Chem Soc Rev 41:6931
14. Matsunaga S, Shibasaki M (2014) Chem Commun 50:1044
15. Esswein AJ, Veige AS, Nocera DG (2005) J Am Chem Soc 127:16641
16. Gray TG, Veige AS, Nocera DG (2004) J Am Chem Soc 126:9760
Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond
95