Cyclopentadienyl ring activation in organometallic chemistry and catalysis

VanderWeide, Andrew; Prokopchuk, Demyan E.

doi:10.1038/s41570-023-00501-1

Cited by 8 publications

(1 citation statement)

References 132 publications

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“…In contrast to ligand scaffolds containing proton-responsive O–H and N–H bonds, using ligand-based C–H bonds for proton-coupled electron transfer (PCET) applications with Earth-abundant metals remains scant. Only recently, C–H bonds within the classic “ancillary” η 5 -cyclopentadienyl (Cp) ligand family have been utilized for PCET chemistry, where the η 5 -Cp ligand is transformed into a dearomatized η 4 -cyclopentadiene (η 4 -CpH) moiety via nucleophilic or electrophilic activation . Peters and co-workers reported that reactions of decamethylcobaltocene (Cp* 2 Co) and decamethylcobatocenium ([Cp* 2 Co] + ) with Brønsted acids and NaBH 4 , respectively, produce (η 4 -Cp*H) intermediates that release potent H • or H – moieties during the Fe-catalyzed reduction of N 2 to NH 3 . − Dempsey and co-workers recently investigated the stoichiometric proton transfer kinetics with piano-stool complexes [CpCo III (diphosphine)(NCMe)] 2+ under reducing conditions to understand the relationship between the kinetics of Co III –H formation and the strength of exogenous acid .…”

Section: Introductionmentioning

confidence: 99%

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes

Goel,

Neugebauer,

VanderWeide

et al. 2023

ACS Catal.

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Cyclopentadienyl (Cp), a classic ancillary ligand platform, can be chemically noninnocent in electrocatalytic H−H bond formation reactions via protonation of coordinated η 5 -Cp ligands to form η 4 -CpH moieties. However, the kinetics of η 5 -Cp ring protonation, ligand-to-metal (or metal-to-ligand) proton transfer, and the influence of solvent during H 2 production electrocatalysis remain poorly understood. We report in-depth kinetic details for electrocatalytic H 2 production with Fe complexes containing amine-functionalized Cp N3 ligands that are protonated via exogenous acid to generate via η 4 -Cp N3 H intermediates (Cp N3 = 6-amino-1,4-dimethyl-5,7-diphenyl-2,3,4,6-tetrahydrocyclopenta[b]pyrazin-6-yl). Under reducing conditions, state-of-the-art DFT calculations reveal that a coordinated solvent plays a crucial role in mediating stereo-and regioselective proton transfer to generate (endo-Cp N3 H)Fe(CO) 2 (NCMe), with other protonation pathways being kinetically insurmountable. To demonstrate regioselective endo-Cp N3 H formation, the isoelectronic model complex (endo-Cp N3 H)Fe(CO) 3 is independently prepared, and kinetic studies with the on-cycle hydride intermediate Cp N3 FeH(CO) 2 under CO cleanly furnish the ring-activated complex (endo-Cp N3 H)Fe(CO) 3 via metal-to-ligand proton migration. The on-cycle complex Cp N3 FeH(CO) 2 reacts with acid to release H 2 and regenerate [Cp N3 Fe(CO) 2 (NCMe)] + , which was found to be the TOF-determining step via DFT. Collectively, these experimental and computational results underscore the emerging importance of Cp ring activation, inner-sphere solvation, and metal−ligand cooperativity to perform proton-coupled electron transfer catalysis for chemical fuel synthesis.

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Section: Introductionmentioning

confidence: 99%

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes

Goel,

Neugebauer,

VanderWeide

et al. 2023

ACS Catal.

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Dihydroguaiazulenide Complexes and Catalysts of Group 8–12 Transition Metals: Ligands from Renewable Feedstock Replace, even Outmatch Petrochemical Based Cyclopentadienyl Chemistry

Vollgraff,

Doppiu,

Sundermeyer

2023

Chemistry A European J

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We present an in‐depth study of the sterically demanding Cp synthon (8‐H‐GuaH)Li isolated from natural product guaiazulene as a ligand transfer reagent towards late transition metal complex precursors. The synthesis and full characterization of selected, essentially unexplored homo‐ and heteroleptic 8‐H‐guaiazulenide complexes of iron, ruthenium, cobalt, rhodium, platinum, copper and zinc are discussed in detail. In order to demonstrate their potential in catalytic applications, [(GuaH)PtMe3] was selected. The latter proved an even higher catalytic activity in light induced olefin hydrosilylation at catalyst loads as low as 5 ppm than classical [CpPtMe3] in a typical test reaction of silicone elastomer fabrication. Our results demonstrate that traditional petrochemical based Cp metal chemistry and catalysis can be replaced, sometimes even outmatched by superior catalysts based on cheap building blocks from renewable feedstock.

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Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

Chamkin,

Chamkina

2024

J Comput Chem

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The present computational study provides a benchmark of density functional theory (DFT) methods in describing hydrogen evolution processes catalyzed by [Cp*Rh]‐containing organometallic complexes. A test set was composed of 26 elementary reactions featuring chemical transformations and bonding situations essential for the field, including the emerging concept of non‐innocent Cp* behavior. Reference values were obtained from a highly accurate 3/4 complete basis set and 6/7 complete PNO space extrapolated DLPNO‐CCSD(T) energies. The performance of lower‐level extrapolation procedures was also assessed. We considered 84 density functionals (DF) (including 13 generalized gradient approximations (GGA), nine meta‐GGAs, 33 hybrids, and 29 double‐hybrids) and three composite methods (HF‐3c, PBEh‐3c, and r2SCAN‐3c), combined with different types of dispersion corrections (D3(0), D3BJ, D4, and VV10). The most accurate approach is the PBE0‐DH‐D3BJ (MAD of 1.36 kcal mol−1) followed by TPSS0‐D3BJ (MAD of 1.60 kcal mol−1). Low‐cost r2SCAN‐3c composite provides a less accurate but much faster alternative (MAD of 2.39 kcal mol−1). The widely used Minnesota‐family M06‐L, M06, and M06‐2X DFs should be avoided (MADs of 3.70, 3.94, and 4.01 kcal mol−1, respectively).

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Cyclopentadienyl ring activation in organometallic chemistry and catalysis

Cited by 8 publications

References 132 publications

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes

Dihydroguaiazulenide Complexes and Catalysts of Group 8–12 Transition Metals: Ligands from Renewable Feedstock Replace, even Outmatch Petrochemical Based Cyclopentadienyl Chemistry

Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

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Cyclopentadienyl ring activation in organometallic chemistry and catalysis

Cited by 8 publications

References 132 publications

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H2 Production with Fe(CpN3) Complexes

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H2 Production with Fe(CpN3) Complexes

Dihydroguaiazulenide Complexes and Catalysts of Group 8–12 Transition Metals: Ligands from Renewable Feedstock Replace, even Outmatch Petrochemical Based Cyclopentadienyl Chemistry

Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

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Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes

Essential Roles of Cp Ring Activation and Coordinated Solvent During Electrocatalytic H₂ Production with Fe(Cp^N3) Complexes