Top Organomet Chem (2021) 68: 71–94
https://doi.org/10.1007/3418_2020_69
# Springer Nature Switzerland AG 2020, corrected publication 2020
Published online: 26 November 2020
Metal-Ligand Cooperativity
of Phosphorus-Containing Pincer Systems
Seji Kim, Yeong-Eun Kim, and Yunho Lee
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2 Electron and Proton Transfer Between Metal and Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3 C-group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4 O-(S-)group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5 N-group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Abstract A metal-bound phosphorus atom can actively participate in various
organometallic reactions as an electron reservoir and/or a group transfer site, because
a phosphorus atom can adopt several distinct forms such as cationic phosphenium,
anionic phosphide, neutral phosphine, or a phosphinyl radical, thus making it more
versatile. Furthermore, the ability of the phosphorus atom to have various oxidation
states promotes the phosphorus atom to be cooperatively engaged in the reaction
occurring at a metal center. By using such properties of phosphorus, metal-ligand
cooperative (MLC) reactions occurring at a P-M moiety embedded in several
transition metal pincer systems are discussed in this chapter.
Keywords Group transfer · Metal-ligand cooperativity · Phosphorus ·
Pincer ligand · Redox active
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_74
S. Kim, Y.-E. Kim, and Y. Lee (*)
Department of Chemistry, Seoul National University, Seoul, South Korea
e-mail: yunhochem@snu.ac.kr
https://doi.org/10.1007/3418_2020_69
# Springer Nature Switzerland AG 2020, corrected publication 2020
Published online: 26 November 2020
Metal-Ligand Cooperativity
of Phosphorus-Containing Pincer Systems
Seji Kim, Yeong-Eun Kim, and Yunho Lee
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2 Electron and Proton Transfer Between Metal and Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3 C-group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4 O-(S-)group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5 N-group Transfer Reactions of a M-P Moiety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Abstract A metal-bound phosphorus atom can actively participate in various
organometallic reactions as an electron reservoir and/or a group transfer site, because
a phosphorus atom can adopt several distinct forms such as cationic phosphenium,
anionic phosphide, neutral phosphine, or a phosphinyl radical, thus making it more
versatile. Furthermore, the ability of the phosphorus atom to have various oxidation
states promotes the phosphorus atom to be cooperatively engaged in the reaction
occurring at a metal center. By using such properties of phosphorus, metal-ligand
cooperative (MLC) reactions occurring at a P-M moiety embedded in several
transition metal pincer systems are discussed in this chapter.
Keywords Group transfer · Metal-ligand cooperativity · Phosphorus ·
Pincer ligand · Redox active
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_74
S. Kim, Y.-E. Kim, and Y. Lee (*)
Department of Chemistry, Seoul National University, Seoul, South Korea
e-mail: yunhochem@snu.ac.kr