ion step. The reactivity of pMMO has been also explored by Chan,525 by means of DFT calculations on small models of Figure 116. Nonradical mechanism proposed in the Yoshizawa model of sMMO. Figure 117. Mononuclear and dinuclear models of the copper active sites of pMMO. CsH Bond Activation in Transition Metal Species Chemical Reviews, 2010, Vol. 110, No. 2 813

C-H bond activation in transition metal species from a computational perspective

Lung Wa Chung,† W. M. C. Sameera,‡ Romain Ramozzi,‡ Alister J. Page, Miho Hatanaka,‡ Galina P. Petrova, Travis V. Harris,‡,⊥ Xin Li, Zhuofeng Ke, Fengyi Liu, Hai-Bei Li, Lina Ding, and Keiji Morokuma*,‡ †Department of Chemistry, South University of Science and Technology of China, Shenzhen 518055, China ‡Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Sakyo, Kyoto 606-8103, Japan Newcastle Institute for Energy and Resources, The University of Newcastle, Callaghan 2308, Australia Faculty of Chemistry and Pharmacy, University of Sofia, Bulgaria Boulevard James Bourchier 1, 1164 Sofia, Bulgaria Department of Chemistry, State University of New York at Oswego, Oswego, New York 13126, United States State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710119, China School of Ocean, Shandong University, Weihai 264209, China School of Pharmaceutical Sciences, Zhengzhou University, 100 Kexue Avenue, Zhengzhou, Henan 450001, China

The ONIOM Method and Its Applications

Functionalization of fluorinated molecules by transition-metal-mediated C-F bond activation to access fluorinated building blocks.

https://escholarship.org/content/qt1kp1t47g/qt1kp1t47g.pdf?t=o0hb1w

Radical ligand-containing single-molecule magnets

Recent computational studies of C–H bond activation at late transition metal systems are discussed and processes where lone pair assistance via heteroatom co-ligands or carboxylates are highlighted as a particularly promising means of cleaving C–H bonds. The term ‘ambiphilic metal ligand activation’ (AMLA) is introduced to describe such reactions.

/pdf/mechanisms-of-c-h-bond-activation-rich-synergy-between-3jgfvvnnbo.pdf

Mechanisms of C–H bond activation: rich synergy between computation and experiment

https://escholarship.org/content/qt6cp108pr/qt6cp108pr.pdf?t=li520x

Preparation and Reactions of Base-Free Bis(1,2,4-tri-tert-butylcyclopentadienyl)uranium Oxide, Cp‘2UO

The net reaction of monomeric Cp‘2CeH [Cp‘ = 1,3,4-(Me3C)3(C5H2)] in C6D6 with C6F6 is Cp‘2CeF, H2, and tetrafluorobenzyne. The pentafluorophenylmetallocene, Cp‘2Ce(C6F5), is formed as an intermediate that decomposes slowly to Cp‘2CeF and C6F4 (tetrafluorobenzyne), and the latter is trapped by the solvent C6D6 as a [2+4] cycloadduct. In C6F5H, the final products are also Cp‘2CeF and H2, which are formed from the intermediates Cp‘2Ce(C6F5) and Cp‘2Ce(2,3,5,6-C6F4H) and from an unidentified metallocene of cerium and the [2+4] cycloadducts of tetra- and trifluorobenzyne with C6D6. The hydride, fluoride, and pentafluorophenylmetallocenes are isolated and characterized by X-ray crystallography. DFT(B3PW91) calculations have been used to explore the pathways leading to the observed products of the exergonic reactions. A key step is a H/F exchange reaction which transforms C6F6 and the cerium hydride into C6F5H and Cp‘2CeF. This reaction starts by an η1-F−C6F5 interaction, which serves as a hook. The reaction pr...

Hydrogen for fluorine exchange in C6F6 and C6F5H by monomeric [1,3,4-(Me3C)3C5H2]2CeH: experimental and computational studies.

Hydrogen for Fluorine Exchange in C 6 F 6 and C 6 F 5 H by Monomeric [1,3,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH: Experimental and Computational Studies

Synthesis and Structural Characterization of the First Uranium Cluster Containing an Isopolyoxometalate Core

Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bis(pentamethylcyclopentadienyl)ytterbium, Cp2*Yb (Mex-bipy). In contrast to Cp2*Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal X-ray diffraction (XRD), the temperature dependence of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp2*Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.

/pdf/intermediate-valence-tautomerism-in-decamethylytterbocene-449mt1aqh1.pdf

Evan L. Werkema

Papers

Preparation and Reactions of Base-Free Bis(1,2,4-tri-tert-butylcyclopentadienyl)uranium Oxide, Cp‘2UO

Hydrogen for fluorine exchange in C6F6 and C6F5H by monomeric [1,3,4-(Me3C)3C5H2]2CeH: experimental and computational studies.

Hydrogen for Fluorine Exchange in C 6 F 6 and C 6 F 5 H by Monomeric [1,3,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH: Experimental and Computational Studies

Synthesis and Structural Characterization of the First Uranium Cluster Containing an Isopolyoxometalate Core

Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines