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).

/pdf/secondary-building-units-nets-and-bonding-in-the-chemistry-o0m4ttzsgz.pdf

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

Transition-metal cluster chemistry: reactions of manganese dimer ion (mn2+) with molecular oxygen

The hydrogen atom transfer reactions of helium(1+) and neon(1+) ions with isotopic molecular hydrogen (H2, D2, and HD) are investigated using guided ion beam techniques. These reactions are exothermic, but are known to be extremely slow at thermal energies. The cross sections for formation of HeH+ (HeD+) and NeH+ (NeD+) exhibit thresholds at high relative translational energies, 8 to 12 eV c.m. Unusual isotope effects are observed in the reaction with HD. The deuteride product is formed exclusively near threshold, while the hydride product predominates at higher energies. Reaction mechanisms involving Rydberg excited states of HeH+2 and NeH+2 are discussed.

Hydrogen atom transfer reactions of He+ and Ne+ with H2, D2, and HD

In previous work, guided ion beam tandem mass spectrometry has been used to study the reactions of the cluster cations of several transition metals (V, Cr, Fe and Ni) with D2, O2, CO2 and CD4. By examining the kinetic energy dependence of these reactions and interpreting thresholds observed for various reactions, bond energies for D, O, C, CD, CD2 and CD3 can be obtained. The results of these studies are reviewed with an emphasis on the relationship between the thermochemistry obtained from this work with that for adsorbates on bulk-phase metal surfaces. It is found that in cases where quantitative comparison can be made, for example D and O atoms, modest sized clusters bind these species to approximately the same extent as the bulk-phase surface of the same metal. As there is little information available for the molecular fragments investigated here, the cluster bond energies provide some of the first experimental values for such adsorbates on surfaces.

The thermochemistry of adsorbates on transition metal cluster ions: relationship to bulk-phase properties.

Spin–orbit state‐selected reactions of Xe+(2PJ ), J=3/2 and 1/2, with isotopic molecular hydrogen (H2, D2, and HD) to form XeH+ and XeD+ are studied using guided ion beam mass spectrometry. Reaction cross sections are determined as a function of reactant kinetic energy from near thermal energy to 15 eV c.m. Although the reaction of Xe+(2P1/2)+H2 to form ground state products XeH++H is exothermic, no reaction is observed at low energies and the reaction cross section is zero or small at higher energies. The Xe+(2P3/2)+H2 reaction has an apparent threshold near its endothermicity, but the cross section rises slowly above this threshold. The reaction energetics and isotope effects indicate two separate mechanisms for Xe+(2P3/2). The dominant mechanism is a direct, impulsive process with an apparent activation barrier. The second mechanism allows reaction near the thermochemical threshold and involves more interaction among all three atoms. These results are interpreted in relation to the spin–orbit coupled p...

Spin–orbit state‐selected reactions of Xe+(2P3/2 and 2P1/2) with H2, D2, and HD

The deamidation and dehydration products of Na+(L), where L = asparagine (Asn), glutamine (Gln), aspartic acid (Asp), and glutamic acid (Glu), are examined in detail utilizing collision-induced dissociation (CID) with Xe in a guided ion beam tandem mass spectrometer (GIBMS). Results establish that the Na+(L) complexes decompose upon formation in our dc discharge/flow tube ion source to form a bis-ligand complex, Na+(L−HX)(HX), composed of a sodium cation, the (L−HX) decomposition product, and HX, where HX = NH3 for the amides and H2O for the acids. Analysis of the energy-dependent CID cross sections for the Na+(L−HX)(HX) complexes provides unambiguous identification of the (L−HX) fragmentation products as 3-amino succinic anhydride (a-SA) for Asx and oxo-proline (O-Pro) for Glx. Furthermore, these experiments establish the 0 K sodium cation affinities for these five-membered ring decomposition products and the H2O and NH3 binding affinities of the Na+(a-SA) and Na+(O-Pro) complexes after accounting for un...

Experimental and Theoretical Studies of Sodium Cation Complexes of the Deamidation and Dehydration Products of Asparagine, Glutamine, Aspartic Acid, and Glutamic Acid

P. B. Armentrout

Papers

Transition-metal cluster chemistry: reactions of manganese dimer ion (mn2+) with molecular oxygen

Hydrogen atom transfer reactions of He+ and Ne+ with H2, D2, and HD

The thermochemistry of adsorbates on transition metal cluster ions: relationship to bulk-phase properties.

Spin–orbit state‐selected reactions of Xe+(2P3/2 and 2P1/2) with H2, D2, and HD

Experimental and Theoretical Studies of Sodium Cation Complexes of the Deamidation and Dehydration Products of Asparagine, Glutamine, Aspartic Acid, and Glutamic Acid