Reactivity of Hydride Bridges in High-Spin [3M-3(μ-H)] Clusters (M = FeII, CoII).
The designed [3M-3(μ-H)] clusters (M = Fe(II), Co(II)) Fe3H3L (1-H) and Co3H3L (2-H) [where L(3-) is a tris(β-diketiminate) cyclophane] were synthesized by treating the corresponding M3Br3L complexes with KBEt3H. From single-crystal X-ray analysis, the hydride ligands are sterically protected by the cyclophane ligand, and these complexes selectively react with CO2 over other unsaturated substrates (e.g., CS2, Me3SiCCH, C2H2, and CH3CN). The reaction of 1-H or 2-H with CO2 at room temperature yielded Fe3(OCHO)(H)2L (1-CO2) or Co3(OCHO)(H)2L (2-CO2), respectively, which evidence the differential reactivity of the hydride ligands within these complexes. The analogous reactions at elevated temperatures revealed a distinct difference in the reactivity pattern for 2-H as compared to 1-H; Fe3(OCHO)3L (1-3CO2) was generated from 1-H, while 2-H afforded only 2-CO2.
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
Yousoon
Y
Lee
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
Kevin J
KJ
Anderton
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
Forrest T
FT
Sloane
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
David M
DM
Ermert
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
Khalil A
KA
Abboud
Université Grenoble Alpes, LCBM/PMB and CEA, iRTSV/CBM/PMB and CNRS, UMR 5249, LCBM/PMB, 38000 Grenoble, France.
Ricardo
R
García-Serres
Center for Catalysis and Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
Leslie J
LJ
Murray