Transition Metal Carbide Complexes
Publikation: Bidrag til tidsskrift › Review › Forskning › fagfællebedømt
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Transition Metal Carbide Complexes. / Reinholdt, Anders; Bendix, Jesper.
I: Chemical Reviews, Bind 122, Nr. 1, 2022, s. 830–902.Publikation: Bidrag til tidsskrift › Review › Forskning › fagfællebedømt
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TY - JOUR
T1 - Transition Metal Carbide Complexes
AU - Reinholdt, Anders
AU - Bendix, Jesper
N1 - Publisher Copyright: ©
PY - 2022
Y1 - 2022
N2 - Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating LnM-CEx fragments, followed by cleavage of the C-E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide-carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C1 reagents, engage in cross-coupling reactions, and enact Fischer-Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.
AB - Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating LnM-CEx fragments, followed by cleavage of the C-E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide-carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C1 reagents, engage in cross-coupling reactions, and enact Fischer-Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.
U2 - 10.1021/acs.chemrev.1c00404
DO - 10.1021/acs.chemrev.1c00404
M3 - Review
C2 - 34797626
AN - SCOPUS:85120380989
VL - 122
SP - 830
EP - 902
JO - Chemical Reviews
JF - Chemical Reviews
SN - 0009-2665
IS - 1
ER -
ID: 286858065