Low-valent iron: an Fe(I) ate compound as a building block for a linear trinuclear Fe cluster.

A low-valent trinuclear iron complex with an unusual linear Fe(I)-Fe(II)-Fe(I) unit is presented. It is accessed in a rational approach using a salt metathesis reaction between a new anionic Fe(I) containing heterocycle and FeCl2. Its electronic structure was studied by single crystal XRD analysis, EPR and Mössbauer spectroscopy, and magnetic susceptibility measurements.

Energy and chemicals from the selective electrooxidation of renewable diols by organometallic fuel cells.

Organometallic fuel cells catalyze the selective electrooxidation of renewable diols, simultaneously providing high power densities and chemicals of industrial importance. It is shown that the unique organometallic complex [Rh(OTf)(trop2NH)(PPh3)] employed as molecular active site in an anode of an OMFC selectively oxidizes a number of renewable diols, such as ethylene glycol , 1,2-propanediol (1,2-P), 1,3-propanediol (1,3-P), and 1,4-butanediol (1,4-B) to their corresponding mono-carboxylates. The electrochemical performance of this molecular catalyst is discussed, with the aim to achieve cogeneration of electricity and valuable chemicals in a highly selective electrooxidation from diol precursors.

Pi-donation and stabilizing effects of pnicogens in carbenium and silicenium ions: a theoretical study of [C(XH2)3]+ and [Si(XH2)3]+ (X = N, P, As, Sb, Bi).

Quantum chemical calculations at the MP2 and CCSD(T) levels of theory are reported for cations of the general type [A(XH2)3]+ with A = C, Si and X = N, P, As, Sb, Bi. Population analysis, methyl stabilization energies (MSEs), and structural criteria were used to predict the p(pi)-donor ability of and the pi-stabilization energy exerted by this series of pnicogens. All of the substituents XH2 considered in these studies invariably stabilize the triply substituted carbenium as well as the silicenium ions. The calculated data show that the intrinsic p(pi)-donation of the group 15 atoms follows the order N < P < As < Sb < Bi. However, the trend of the stabilization energies is fully reversed. The intrinsic stabilization energies of the planar carbenium ions decrease monotonically from 161.2 kcal mol(-1) for X = NH2 to 98.0 kcal mol(-1) for X = BiH2. The effective stabilization of the pnicogens in the equilibrium structures, which also includes the energy-demanding pyramidalization of the XH2 substituents, follows the same trend, although the absolute numbers are reduced to 145.6 kcalmol(-1) for X = NH2 and 53.2 kcalmol(-1) for X = BiH2. This seemingly contrasting behavior of increasing p(pi) charge donation and decreasing stabilization has already been found for other substituents. Previous studies have shown that carbenium ions substituted by chalcogens up to the fourth row also stabilize C+ less effectively with respect to heavier substituents. Of the ions investigated in this study, only the silicenium ions that are stabilized by pnicogens from the third to the sixth row of the periodic system yield increased stabilizing energies that follow the corresponding intrinsic p(pi)-donor abilities of the respective substituent.

A study of gas-phase reactions of radical cations of mono- and dihaloethenes with alcohols by FT-ICR spectrometry and molecular orbital calculations: substitution versus oxidation.

The ion-molecule reactions of the radical cations of vinyl chloride (1), vinyl bromide (2), 1,2-dichloroethene (3), 1,2-dibromoethene (4), 1,1-dichloroethene (5), and 1,1-dibromoethene (6) with methanol (MeOH) and ethanol (EtOH) have been studied by FT-ICR spectrometry. In the case of EtOH as reactant the oxidation of the alcohol to protonated acetaldehyde by a formal hydride transfer to the haloethene radical cation is the main process if not only reaction observed with the exception of the 1,2-dibromoethene radical cation which exhibits slow substitution. In secondary reactions the protonated acetaldehyde transfers the proton to EtOH which subsequently undergoes a well known condensation reaction of EtOH to form protonated diethyl ether. With MeOH as reactant, the 1,2-dihaloethene radical cations of 3.+ and 4.+ exhibit no reaction, while the other haloethene radical cations undergo the analogous reaction sequence of oxidation yielding protonated formaldehyde. Generally, bromo derivatives of haloethene radical cations react predominantly by substitution and chloro derivatives by oxidation. This selectivity can be understood by the thermochemistry of the competing processes which favors substitution of Br while the effect of the halogen substituent on the formal hydride transfer is small. However, the bimolecular rate constants and reaction efficiencies of the total reactions of the haloethene radical cations with both alcohols exhibit distinct differences, which do not follow the exothermicity of the reactions. It is suggested that the substitution reaction as well as the oxidation by formal hydride transfer proceeds by mechanisms which include fast and reversible addition of the alcohol to the ionized double bond of the haloethene radical cation which generates a beta-distonic oxonium ion as the crucial intermediate. This intermediate is energetically excited by the exothermic addition and fragments either directly by elimination of a halogen substituent to complete the substitution process or rearranges by hydrogen migration before dissociation into the protonated aldehyde and a beta-haloethyl radical. Reversible addition and hydrogen migrations within a long lived intermediate is proven experimentally by H/D exchange accompanying the reaction of the radical cations of vinyl chloride (1) and 1,1-dichloroethene (5) with CD3OH. The suggested mechanisms are substantiated by ab initio molecular orbital calculations.

Topographical analyses of homonuclear multiple bonds between main group elements

Recent experiments have resulted in the completion of the series of Group 14 and Group 15 element double-bond systems, R(n)E=ER(n) (E = C - Pb, n = 2; E = N - Bi, n = 1). Furthermore, new families of multiple-bonded species have been discovered, such as the radical anion [RSnSnR](-) , the close ion pairs [RE(mu2Na)2ER] (E = Ge,Sn), and a digallyne [RGa(mu2Na)2GaR] for which a Ga=Ga triple bond was formulated. Some of these compounds show classical multiple bond features (i.e. the dipnictogens RE=ER, E=N-Bi) in the sense that planar structures with short E-E distances are observed. However, many (i.e. R2E=ER2, E = Si - Pb) do not behave as expected for compounds with multiple bonds. They have trans bent structures, show enormous variation in their E-E distances, and some dissociate easily under E-E bond cleavage in solution. These properties raised doubts as to whether these compounds can be formulated as multiple-bonded systems. Using the electron localization function (ELF) it is possible to clearly show the topographical similarities between classical and nonclassical multiple bonds; ELF divides these systems into unslipped (classical) and slipped (nonclassical) systems. ELF can also be employed to confirm the nonexistence of multiple bonds. Therefore, topographical analyses using ELF are useful to categorize a bonding system. In particular, the bonds in the heavier Group 14 double systems and the Ga-Ga bond in digallyne are clearly shown by this method as slipped double and triple bonds, respectively.

CHEMISTRY: New Chemical Bricks Made Through Phosphorus Tricks.

One approach for stabilizing chemical compounds that would exist only fleetingly or not at all is to substitute an analog for one of the atoms that better accommodates the structure to be formed. Grützmacher reviews one approach (including recent work reported by Kato et al.) that he dubs "the phosphorus trick," in which phosphorus, by substituting for nitrogen, not only stabilizes compounds but allows several chemical reactions to proceed more readily.

Strong P=P pi Bonds: The First Synthesis of a Stable Phosphanyl Phosphenium Ion.

A 35-fold excess of methyl triflate (2) is required to quantitively prepare 3, the first phosphanyl phosphenium ion, from diphosphene 1. Experimental data and calculations indicate that the P=P bond becomes stronger upon alkylation.

Liquid secondary ion mass spectrometry of methyl glycosides of oligosaccharides using matrices containing carboxamides.

Intense cluster ions corresponding to proton-bound hetero-dimers of an amide molecule and an oligosaccharide molecule are observed in the liquid secondary ion mass spectra of methyl glycosides of oligoxylans if a solution of an aliphatic carboxamide in glycerol is used as the liquid matrix. These cluster ions are particularly abundant and persist for a long period if urea (U) or thiourea (TU) is used as the matrix additive. In these cases, cluster ions containing more than one molecule of U or TU and two oligosaccharide molecules are also observed. The intense signal due to the proton-bound hetero-dimer between U or TU and the oligosaccharide can be used with advantage for a molecular weight determination. The bonding interactions between a protonated saccharide molecule and a molecule U or TU in the proton-bound hetero-dimers are so strong that the urea molecules remain attached to the fragment ions during the decay of metastable cluster ions and even during collision-induced dissociation. Thus, the mass-analysed ion kinetic energy spectra of these proton-bound hetero-dimers are dominated by abundant cluster ions [Bn+U] and [Ym+U] arising from cleavage of the glycosidic bonds within the oligosaccharides. The collisionally-activated mass spectra of the proton-bound hetero-dimers additionally contain peaks of the free ions Bn and Ym. Therefore, these spectra clearly reflect the arrangement of the monosaccharide residues in the oligosaccharide and can be used conveniently for structural analysis.

Dissociation of proton-bound complexes and proton affinity of benzamides.

Proton-bound heterodimers of substituted benzamides 1-15 and N,N-dimethyl benzamides 16-30, respectively, with a series of reference bases were generated under chemical ionization conditions. Their dissociation into the protonated amide AH(+) and protonated reference base BH(+) was studied by metastable ion techniques and by collision-induced dissociation (CID) to examine substituent effects on the proton affinity (PA) of the benzarnides and to elucidate some aspects of the dissociation dynamics of proton-bound clusters. The PAs of the substituted benzarnides were determined by bracketing the amide by a pair of reference bases to give rise to more and less abundant signals of the protonated base in the mass-analyzed ion kinetic energy (MIKE) spectra of the proton-bound heterodimers. The substituent effects observed agree with O-protonation in both the primary and the tertiary benzamides. However, the susceptibility of the benzamide to polar substituent effects is remarkably small, which indicates a "resonance saturation"), of the amide group. The relative abundances of AH(+) and BH(+) in the MIKE and collisional activation (CA) mass spectra depend strongly on the pressure of the collision gas during CID, and in certain cases a reversal of the relative abundances with increasing pressure that favors the formation of BH+ from a less basic reference base is observed. Although this effect underlines the limited possibilities of the "kinetic method" for PA determination by CID of proton-bound heterodimers, it uncovers important kinetic effects during the dissociation of proton-bound heterodimers and of proton transfer reactions in the gas phase.. In the case of the protonated amide clusters, the observed intensity effects in the CA mass spectra are explained by a double-well potential energy surface caused by solvation of the protonated base by the polar amide in the protonated heterodimer.

Positional identification of fluorine in methyl per-O-acetyl-x-deoxy-x-fluoro-alpha-D-hexopyranosides by electron impact and chemical ionisation mass spectrometry.

Fully acetylated methyl x-deoxy-x-fluoro-alpha-D-glucopyranosides have been studied using electron impact and ammonia chemical ionisation mass spectrometry. Mass analysed metastable ion kinetic energy spectroscopy (MIKE), collisional activation (CID), and accelerated voltage scanning have been used to evaluate complete fragmentation schemes. Characteristic differences in the fragmentation of positional isomers were noted on analysis of the spectra, and these make it possible to determine the location of fluorine in the molecules studied. Collisionally activated fragmentation of [M-OCH3]+ ions, produced by electron impact, provides an alternative method for localisation of the fluorine atoms. To the contrary, MIKE and CID spectra of [M + NH4]+ cluster ions produced by chemical ionisation did not afford such structural information.

Remote fragmentations of protonated aromatic carbonyl compounds via internal reactions in intermediary ion-neutral complexes.

Protonated aromatic aldehydes and methyl ketones 1a-10a, carrying initially the proton at the carbonyl group, are prepared by electron impact-induced loss of a methyl radical from 1-arylethanols and 2-aryl-2-propanols, respectively. The aryl moiety of the ions corresponds to a benzene group, a naphthalene group, a phenanthrene group, a biphenyl group, and a terphenyl group. respectively, each substituted by a CH3OCH2 side-chain as remote from the acyl substituent as possible. The characteristic reactions of the metastable ions, studied by mass-analyzed ion kinetic energy spectrometry, are the elimination of methanol, the formation of CH3OCH 2 (+) ions, and the elimination of an ester RCOOCH3 (R = H and CH3) . The mechanisms of these fragmentations were studied by using D-labeled derivatives. Confirming earlier results, it is shown that the ester elimination, at least from the protonated aryl methyl ketones, has to proceed by an intermediate [acyl cation/arylmethyl methyl ether]-complex. The relative abundances of the elimination of methanol and of the ester decrease and increase, respectively, with the size of the aromatic system. Clearly, the fragmentation via intermediate ion-neutral complexes is favored for the larger ions. Furthermore, the acyl cation of these complexes can move unrestricted over quite large molecular distances to react with the remote CH3OCH2-side-chain, contrasting the restricted migration of a proton by 1,2-shifts ("ring walk") in these systems.