ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

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Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

https://anthropology.ucsd.edu/_files/Faculty%20Files/schoeninger-publications/DeNiro-Schoeninger1984.pdf

Nitrogen and carbon isotopic composition of bone collagen from marine and terrestrial animals

Publisher Summary The chapter focuses on a general description of the force fields that are most commonly used at present, and it gives an indication of the directions of current research that may yield better functions in the near future. After a brief survey of current models, mostly generated during the 1990s, the focus of the chapter is on the general directions the field is taking in developing new models. The most commonly used protein force fields incorporate a relatively simple potential energy function: The emphasis is on the use of continuum methods to model the electrostatic effects of hydration and the introduction of polarizability to model the electronic response to changes in the environment. Some of the history and performance of widely used protein force fields based on an equation on simplest potential energy function or closely related equations are reviewed. The chapter outlines some promising developments that go beyond this, primarily by altering the way electrostatic interactions are treated. The use of atomic multipoles and off-center charge distributions, as well as attempts to incorporate electronic polarizability, are also discussed in the chapter.

https://dasher.wustl.edu/ponder/papers/advprotchem-66-27-03.pdf

Force fields for protein simulations

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Cross sections for the reactions of Ar+ with H2, D2, and HD to form ArH+ and ArD+ are measured using a new guided ion beam tandem mass spectrometer which affords an experimental energy range from 0.05 to 500 eV laboratory. The apparatus and experimental techniques are described in detail. Cross sections for H2 and D2 are found to be nearly identical over this entire energy range when compared at the same barycentric energy. The total HD cross section is the same as H2 and D2 at low energies, but differs significantly above 4 eV c.m., where product dissociation becomes important. The intramolecular isotope effect for reaction with HD exhibits a reversal at low energy, favoring the deuteride product below ∼0.14 eV c.m., and surprising nonmonotonic behavior at energies above 5 eV c.m. In all these systems, a new feature at higher energies is observed. This is interpreted as the onset of a product channel having an energy barrier of 8±1 eV. The room temperature rate constant derived from the data for the reac...

Translational energy dependence of Ar++XY→ArX++Y (XY=H2,D2,HD) from thermal to 30 eV c.m.

Analysis of the energy dependence of the cross sections for collision-induced dissociation reactions has permitted the determination of quantitative thermodynamic information for a variety of ionic clusters. As such clusters become larger, the rate at which the decomposition occurs becomes comparable to the instrumental time available for observing the reaction. A method for incorporating statistical theories for energy-dependent unimolecular decomposition in this threshold analysis is reviewed and updated. The revision relies on the fact that for most ionic clusters, the transition state is a loose association of the products that can be located at the centrifugal barrier. This permits a straightforward estimation of the molecular parameters needed in statistical theories for the transition state. Further, we also discuss several treatments of the adiabatic rotations of the dissociating cluster. The various models developed here and previously are compared and used to analyze a series of data for Li+(ROH...

Statistical modeling of collision-induced dissociation thresholds

Thresholds for collision-induced dissociation of M^+(H_2O), (x = 1-4, M = Ti to Cu) with xenon are measured by using guided ion beam mass spectrometry. In all cases, the primary product is endothermic loss of one water molecule. The cross-section thresholds are interpreted to yield 0 K bond energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the clusters, and dissociation lifetimes. Overall, the results presented here are consistent with previously reported values for x = 1 and 2 and resolve several discrepancies in these values. Theory is shown to accurately predict the BDEs of x = 1 and 2 as well as the sign of the difference between them. For all ions but Mn^+, the bond dissociation energies (BDEs) of the first and second water molecules are large compared with those of the third and fourth water molecules. Trends in BDEs are discussed in terms of hybridization and spin changes occurring at the transition metal center.

Solvation of Transition Metal Ions by Water. Sequential Binding Energies of M+(H2O)x (x = 1-4) for M = Ti to Cu Determined by Collision-Induced Dissociation

Sequential bond energies of Fe(CO)x + (x = 1-5): Systematic effects on collision-induced dissociation measurements

This review focuses on noncovalent metal ion-ligand complexes and measurements of the bond energies of such species. The method utilized in this work is threshold collision-induced dissociation (CID), as achieved using a guided ion beam tandem mass spectrometer. Accurate determination of bond energies requires attention to many details of the experiments and data analysis. These details are discussed thoroughly and compared to other methods. A comprehensive listing of metal-ligand bond dissociation energies determined by threshold CID is provided. This list includes a variety of metals (alkalis, magnesium, aluminum, and first and second row transition metals), many different types of ligands, and variations in the number of ligands. The trends in these values are discussed, and we elucidate the importance of ion-dipole and ion-induced dipole interactions, chelation, different conformers and tautomers, steric interactions, solvation phenomena, and electronic effects such as hybridization and promotion.

P. B. Armentrout

Papers

Translational energy dependence of Ar++XY→ArX++Y (XY=H2,D2,HD) from thermal to 30 eV c.m.

Statistical modeling of collision-induced dissociation thresholds

Solvation of Transition Metal Ions by Water. Sequential Binding Energies of M+(H2O)x (x = 1-4) for M = Ti to Cu Determined by Collision-Induced Dissociation

Sequential bond energies of Fe(CO)x + (x = 1-5): Systematic effects on collision-induced dissociation measurements

Noncovalent metal–ligand bond energies as studied by threshold collision‐induced dissociation