in various organometallic reactions occurring at a metal center. The redox-coupled
geometric alteration of the phosphorus atom located at the center of pincer systems
enables a new way to operate the metal-ligand cooperativity. A phosphorus-based
orbital can be found in the frontier molecular orbitals of first row transition metal
complexes, thus suggesting that electron exchange can occur within a P-M moiety
during a chemical reaction. By utilizing such cooperation between a phosphorus
atom and a metal center in pincer ligand systems, the role of transition metal
complexes in valuable catalytic reactions can be further extended.
Acknowledgments This work was supported by C1 Gas Refinery Program (NRF2015M3D3
A1A01064880).
References
1. Tolman CA (1970) Phosphorus ligand exchange equilibria on zerovalent nickel. A dominant
role for steric effects. J Am Chem Soc 92:2956–2965
2. Quin LD, Verkade JG (eds) (1994) Phosphorus-31 NMR spectral properties in compound
characterization and structural analysis. VCH Publishers, New York
3. Rittle J, Green MT (2010) Cytochrome P450 compound I: capture, characterization, and C–H
bond activation kinetics. Science 330:933–937
4. Yamada H, Siems WF, Koike T, Hurst JK (2004) Mechanisms of water oxidation catalyzed by
the cis,cis-[(bpy) 2 Ru(OH 2 )] 2 O
4+ ion. J Am Chem Soc 126:9786–9795
5. Hurst JK, Cape JL, Clark AE, Das S, Qin C (2008) Mechanisms of water oxidation catalyzed by
ruthenium diimine complexes. Inorg Chem 47:1753–1764
6. Cape JL, Lymar SV, Lightbody T, Hurst JK (2009) Characterization of intermediary redox
states of the water oxidation catalyst, [Ru(bpy) 2 (OH 2 )] 2 O
4+ . Inorg Chem 48:4400–4410
7. Kobayashi K, Ohtsu H, Wada T, Kato T, Tanaka K (2003) Characterization of a stable
ruthenium complex with an oxyl radical. J Am Chem Soc 125:6729–6739
8. Lippert CA, Arnstein SA, Sherrill D, Soper JD (2010) Redox-active ligands facilitate bimetallic
O 2 homolysis at five-coordinate oxorhenium(V) centers. J Am Chem Soc 132:3879–3892
9. Dzik WI, van der Vlugt JI, Reek JNH, de Bruin B (2011) Ligands that store and release
electrons during catalysis. Angew Chem Int Ed 50:3356–3358
10. Lippert CA, Hardcastle KI, Soper JD (2011) Harnessing redox-active ligands for low-barrier
radical addition at oxorhenium complexes. Inorg Chem 50:9864–9878
11. Chaudhuri P, Hess M, Müller J, Hildenbrand K, Bill E, Weyhermüller T, Wieghardt K (1999)
Aerobic oxidation of primary alcohols (including methanol) by copper(II)– and zinc(II)–
phenoxyl radical catalysts. J Am Chem Soc 121:9599–9610
12. Khusnutdinova JR, Milstein D (2015) Metal–ligand cooperation. Angew Chem Int Ed
54:12236–12273
13. Gudat D (1997) Cationic low coordinated phosphorus compounds as ligand: recent development. Coord Chem Rev 163:71–106
14. Caputo CA, Jennings MC, Tuononen HM, Jones ND (2009) Phospha-Fischer carbenes:
synthesis, structure, bonding, and reactions of Pd(0)– and Pt(0)–phosphenium complexes.
Organometallics 28:990–1000
15. Adhikari D, Mossin S, Basuli F, Dible FR, Chipara M, Fan H, Hoffman JC, Meyer K, Mindiola
DJ (2008) A dinuclear Ni(I) system having a diradical Ni2N2 diamond core resting state:
synthetic, structural, spectroscopic elucidation, and reductive bond splitting reactions. Inorg
Chem 47:10479–10490
Metal-Ligand Cooperativity of Phosphorus-Containing Pincer Systems
91
geometric alteration of the phosphorus atom located at the center of pincer systems
enables a new way to operate the metal-ligand cooperativity. A phosphorus-based
orbital can be found in the frontier molecular orbitals of first row transition metal
complexes, thus suggesting that electron exchange can occur within a P-M moiety
during a chemical reaction. By utilizing such cooperation between a phosphorus
atom and a metal center in pincer ligand systems, the role of transition metal
complexes in valuable catalytic reactions can be further extended.
Acknowledgments This work was supported by C1 Gas Refinery Program (NRF2015M3D3
A1A01064880).
References
1. Tolman CA (1970) Phosphorus ligand exchange equilibria on zerovalent nickel. A dominant
role for steric effects. J Am Chem Soc 92:2956–2965
2. Quin LD, Verkade JG (eds) (1994) Phosphorus-31 NMR spectral properties in compound
characterization and structural analysis. VCH Publishers, New York
3. Rittle J, Green MT (2010) Cytochrome P450 compound I: capture, characterization, and C–H
bond activation kinetics. Science 330:933–937
4. Yamada H, Siems WF, Koike T, Hurst JK (2004) Mechanisms of water oxidation catalyzed by
the cis,cis-[(bpy) 2 Ru(OH 2 )] 2 O
4+ ion. J Am Chem Soc 126:9786–9795
5. Hurst JK, Cape JL, Clark AE, Das S, Qin C (2008) Mechanisms of water oxidation catalyzed by
ruthenium diimine complexes. Inorg Chem 47:1753–1764
6. Cape JL, Lymar SV, Lightbody T, Hurst JK (2009) Characterization of intermediary redox
states of the water oxidation catalyst, [Ru(bpy) 2 (OH 2 )] 2 O
4+ . Inorg Chem 48:4400–4410
7. Kobayashi K, Ohtsu H, Wada T, Kato T, Tanaka K (2003) Characterization of a stable
ruthenium complex with an oxyl radical. J Am Chem Soc 125:6729–6739
8. Lippert CA, Arnstein SA, Sherrill D, Soper JD (2010) Redox-active ligands facilitate bimetallic
O 2 homolysis at five-coordinate oxorhenium(V) centers. J Am Chem Soc 132:3879–3892
9. Dzik WI, van der Vlugt JI, Reek JNH, de Bruin B (2011) Ligands that store and release
electrons during catalysis. Angew Chem Int Ed 50:3356–3358
10. Lippert CA, Hardcastle KI, Soper JD (2011) Harnessing redox-active ligands for low-barrier
radical addition at oxorhenium complexes. Inorg Chem 50:9864–9878
11. Chaudhuri P, Hess M, Müller J, Hildenbrand K, Bill E, Weyhermüller T, Wieghardt K (1999)
Aerobic oxidation of primary alcohols (including methanol) by copper(II)– and zinc(II)–
phenoxyl radical catalysts. J Am Chem Soc 121:9599–9610
12. Khusnutdinova JR, Milstein D (2015) Metal–ligand cooperation. Angew Chem Int Ed
54:12236–12273
13. Gudat D (1997) Cationic low coordinated phosphorus compounds as ligand: recent development. Coord Chem Rev 163:71–106
14. Caputo CA, Jennings MC, Tuononen HM, Jones ND (2009) Phospha-Fischer carbenes:
synthesis, structure, bonding, and reactions of Pd(0)– and Pt(0)–phosphenium complexes.
Organometallics 28:990–1000
15. Adhikari D, Mossin S, Basuli F, Dible FR, Chipara M, Fan H, Hoffman JC, Meyer K, Mindiola
DJ (2008) A dinuclear Ni(I) system having a diradical Ni2N2 diamond core resting state:
synthetic, structural, spectroscopic elucidation, and reductive bond splitting reactions. Inorg
Chem 47:10479–10490
Metal-Ligand Cooperativity of Phosphorus-Containing Pincer Systems
91