Chapter 3
FLP Reduction of Carbon Monoxide
and Related Reactions
Tongdao Wang, Constantin G. Daniliuc, Gerald Kehr, and Gerhard Erker
Abstract Frustrated Lewis pairs (FLPs) show some small molecule binding features
that are remotely reminiscent of metal/ligand coordination. This is illustrated by
examples of synergic binding of carbon monoxide (CO) or nitric oxide (NO) to the
Lewis acid/Lewis base pairs of some intramolecular FLP systems. Various pathways
of carbon monoxide reduction at FLP frameworks leading to the formyl stage and
beyond are described. CO reactions at extended FLP systems containing multiple
Lewis acid/Lewis base combinations lead to unusually structured products. The
formation of macrocyclic oligomers upon treatment of some P/B/B FLPs with carbon
monoxide are typical examples. Some carbon monoxide reactions of specifically
substituted d
0 -configurated Group 4 bent metallocene complexes show remarkable
similarities to typical reactions of the metal-free main group element FLPs.
Keywords Frustrated Lewis pairs · Carbon monoxide · CO reduction and
coupling · Macrocyclic oligomers · d
0 -metallocene cations
Abbreviations
9-BBN
9-borabicyclo[3.3.1]nonane
CP MAS cross-polarization magic-angle spinning
Cp
cyclopentadienyl
Cp*
1,2,3,4,5-pentamethylcyclopentadienyl
DFT
density functional theory
Dmesp
2,6-dimesitylphenyl
ESR
electron spin resonance
T. Wang
Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024,
China
C. G. Daniliuc · G. Kehr · G. Erker (B)
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40,
48149 Münster, Germany
e-mail: erker@uni-muenster.de
© Springer Nature Switzerland AG 2021
J. Chris Slootweg and A. R. Jupp (eds.), Frustrated Lewis Pairs,
Molecular Catalysis 2, https://doi.org/10.1007/978-3-030-58888-5_3
87
FLP Reduction of Carbon Monoxide
and Related Reactions
Tongdao Wang, Constantin G. Daniliuc, Gerald Kehr, and Gerhard Erker
Abstract Frustrated Lewis pairs (FLPs) show some small molecule binding features
that are remotely reminiscent of metal/ligand coordination. This is illustrated by
examples of synergic binding of carbon monoxide (CO) or nitric oxide (NO) to the
Lewis acid/Lewis base pairs of some intramolecular FLP systems. Various pathways
of carbon monoxide reduction at FLP frameworks leading to the formyl stage and
beyond are described. CO reactions at extended FLP systems containing multiple
Lewis acid/Lewis base combinations lead to unusually structured products. The
formation of macrocyclic oligomers upon treatment of some P/B/B FLPs with carbon
monoxide are typical examples. Some carbon monoxide reactions of specifically
substituted d
0 -configurated Group 4 bent metallocene complexes show remarkable
similarities to typical reactions of the metal-free main group element FLPs.
Keywords Frustrated Lewis pairs · Carbon monoxide · CO reduction and
coupling · Macrocyclic oligomers · d
0 -metallocene cations
Abbreviations
9-BBN
9-borabicyclo[3.3.1]nonane
CP MAS cross-polarization magic-angle spinning
Cp
cyclopentadienyl
Cp*
1,2,3,4,5-pentamethylcyclopentadienyl
DFT
density functional theory
Dmesp
2,6-dimesitylphenyl
ESR
electron spin resonance
T. Wang
Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024,
China
C. G. Daniliuc · G. Kehr · G. Erker (B)
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstraße 40,
48149 Münster, Germany
e-mail: erker@uni-muenster.de
© Springer Nature Switzerland AG 2021
J. Chris Slootweg and A. R. Jupp (eds.), Frustrated Lewis Pairs,
Molecular Catalysis 2, https://doi.org/10.1007/978-3-030-58888-5_3
87