Search

Collision‐induced dissociation (CID) of the mass‐selected cation [(bipy)Pt(CH3)2(CH2SCH3)]+ in an ion‐trap mass‐spectrometer results in the losses of the neutrals ethane, ethene, dimethyl sulfide, methane, ethyl methyl sulfide, and propane. The generation of the first four neutrals is also observed, when the isolated, dimeric complex [(bipy)Pt(CH3)2(CH2SCH3)]2[SbF6]2 is heated in the condensed phase. While the product distribution is very similar regardless of whether the complex is heated in the solid state or in solution, ethane loss, i. e. the quite rare event of an sp3‐sp3 C−C reductive elimination from a platinum(IV) complex, dominates in the gas‐phase experiment. However, when the counter anion [SbF6]− is exchanged by the more weakly coordinating anion [BAr4F]−, the amounts of ethane and ethene are increased also in the condensed phase. These sum of observations indicates the similarities of the fragmentation of [(bipy)Pt(CH3)2(CH2SCH3)]+ in both phases. Thus, a correlation of processes in both environments is possible for selected systems (and particularly for unimolecular processes), but the choice of the proper conditions is crucial for a meaningful comparison. [ABSTRACT FROM AUTHOR]

The novel bidentate PP and PN ligands o‐(Ph2P)−C6H4−C≡C−PPh2 (LPP) and o‐(Ph2P)−C6H4−4−(C5H9N−Me) (LPN), respectively, have been designed as long‐range "cis‐spanning" ligands for the stabilization of heterodinuclear complexes containing two metal atoms in close proximity. The synthesis of heterodinuclear, formal AuIPtII complexes with the ligand LPP is straightforward. In the course of a one‐pot reaction, a surprisingly high selectivity for the coordination of AuCl and Pt(CNC) (CNC=2,6‐diphenylpyridine‐o,o'‐diate) to the phenyl‐bound and the alkyne‐bound PPh2 sites of LPP is observed, respectively. Chloride abstraction from the resulting heterodinuclear complex [(ClAu)(o‐Ph2P)−C6H4−C≡C−PPh2(Pt{CNC})] with Ag[SbF6] causes metal–metal bond formation and the generation of the cationic complex [LPPAuPt(CNC)][SbF6]. The high site selectivity for the coordination of the two metals to LPP was investigated by stoichiometric reactions of the ligand with one equivalent of the corresponding precursors. While analogous complexation experiments with LPN have not been successful, the synthesis of the heterodinuclear complex [(ClAu)(o‐Ph2P)−C6H4−4‐(C5H9N−Me)(PtCl2{dmso})] and of [LPN(AuCl)2] confirm the ability of LPN to serve as a ditopic ligand. In this context, it is noteworthy that [LPN(AuCl)2] constitutes the first amine–AuCl complex featuring a tertiary amine. [ABSTRACT FROM AUTHOR]

Here, we present a new route to dyes of the BODIPY family. We first built up a N-Boc-protected dipyrromethene scaffold via an aminopalladation cascade. Subsequentially, the pyrrole moiety was deprotected and the BF2 unit inserted. Depending on the terminating reaction, BODIPYs with either aryl or alkynyl moieties were accessible. [ABSTRACT FROM AUTHOR]

In the ion/molecule reaction (IMR) of "rollover"‐cyclometalated [(bipy−H)Pt]+ with (CH3)2S, the loss of C2H4 from the encounter complex was observed as the main process some years ago. The cationic complex [(bipy)Pt(CH2SCH3)]+ was identified as a crucial intermediate by DFT calculations. In order to prove its key role experimentally, the cation has now been generated independently and studied by collision‐induced dissociation (CID). The main process is C2H4 loss, which proves [(bipy)Pt(CH2SCH3)]+ to be an intermediate also in the IMR of [(bipy−H)Pt]+ with (CH3)2S. Based on DFT calculations, the thiomethoxymethyl complexes [(bipy)M(CH2SCH3)]+ (M=Pd and Ni) would also serve as intermediates in the IMRs of [(bipy−H)M]+. While these IMRs cannot be studied explicitly, because the parent ions cannot be generated, the potential intermediate [(bipy)M(CH2SCH3)]+ has been subjected to CID. The main fragmentation channels for both metals corresponds to C2H4 loss. The CID experiments thus provide insights into the hypothetical IMRs of [(bipy−H)M]+ with (CH3)2S. The comparison of the DFT calculations for all three metals Ni, Pd, and Pt with the experimental findings uncovers subtle aspects of the underlying reaction mechanisms. This work highlights the suitability of CID experiments of potential reaction intermediates for the elucidation of reaction mechanisms of IMRs as well as the limitations of this approach. [ABSTRACT FROM AUTHOR]

The article titled "Closing the Gap Between Gas Phase and Condensed Phase: Fragmentation Studies of the Thiomethoxymethyl Complex" in the European Journal of Inorganic Chemistry explores the differences in product distributions between the gas phase and condensed phase environments. The study investigates the influence of aggregation effects, solvent molecules, counter ions, and energy dissipation on these distributions. The authors propose the concept of pseudo-gas-phase conditions as a framework for understanding reactivity transfer. The article provides further details on this research and is authored by B. Butschke and co-workers. [Extracted from the article]

Upon immersion of a lithium (Li) anode into a diluted 0.05 to 0.20 M dimethoxyethane‐solution of the phosphoric acid derivative (CF3CH2O)2P(O)OH (HBFEP), an artificial solid electrolyte interphase (SEI) is generated on the Li‐metal surface. Hence, HBFEP reacts on the surface to the corresponding Li salt (LiBFEP), which is a Li‐ion conducting inorganic coordination polymer. This film exhibits – due to the reversibly breaking ionic bonds – self‐healing ability upon cycling‐induced volume expansion of Li. The presence of LiBFEP as the major component in the artificial SEI is proven by ATR‐IR and XPS measurements. SEM characterization of HBFEP‐treated Li samples reveals porous layers on top of the Li surface with at least 3 μm thickness. Li−Li symmetrical cells with HBFEP‐modified Li electrodes show a three‐ to almost fourfold cycle‐lifetime increase at 0.1 mA cm−2 in a demanding model electrolyte that facilitates fast battery failure (1 M LiOTf in TEGDME). Hence, the LiBFEP‐enriched layer apparently acts as a Li‐ion conducting protection barrier between Li and the electrolyte, enhancing the rechargeability of Li electrodes. [ABSTRACT FROM AUTHOR]

[(Ph3P)AuPt(nbe)3][BAr4F] (nbe = norbornene) constitutes the first olefin-containing, formal Au+IPt0 complex. The unusual coordination mode and the electronic properties have been analyzed spectroscopically and by calculations. The low binding energy of the nbe ligands make this complex a valuable precursor for formal Au+IPt0 complexes and a candidate for heterobimetallic catalysis. [ABSTRACT FROM AUTHOR]

Collision‐induced dissociation (CID) of the mass‐selected cation [(bipy)Pt(CH3)2(CH2SCH3)]+ in an ion‐trap mass‐spectrometer results in the losses of the neutrals ethane, ethene, dimethyl sulfide, methane, ethyl methyl sulfide, and propane. The generation of the first four neutrals is also observed, when the isolated, dimeric complex [(bipy)Pt(CH3)2(CH2SCH3)]2[SbF6]2 is heated in the condensed phase. While the product distribution is very similar regardless of whether the complex is heated in the solid state or in solution, ethane loss, i. e. the quite rare event of an sp3‐sp3 C−C reductive elimination from a platinum(IV) complex, dominates in the gas‐phase experiment. However, when the counter anion [SbF6]− is exchanged by the more weakly coordinating anion [BAr4F]−, the amounts of ethane and ethene are increased also in the condensed phase. These sum of observations indicates the similarities of the fragmentation of [(bipy)Pt(CH3)2(CH2SCH3)]+ in both phases. Thus, a correlation of processes in both environments is possible for selected systems (and particularly for unimolecular processes), but the choice of the proper conditions is crucial for a meaningful comparison. [ABSTRACT FROM AUTHOR]

The reaction of the Ga+ source [Ga(PhF)2]+[Al(ORF)4]− with the neutral σ‐donor ligand dmap (4‐Me2N‐C6H4N) produces the unexpectedly large and fivefold positively charged cluster cation salt [Ga5(dmap)10]5+([Al(ORF)4]−)5. It includes a regular and planar Ga5 pentagon with strong metal–metal bonding. Additionally, the compound represents the first salt in which an ionic 1:5 packing is realized. We discuss the nature of this structure which results from the conversion of the non‐bonding 4s2 lone‐pair orbitals into fully Ga‐Ga‐bonding orbitals and the solid‐state arrangement of the ions constituting the lattice as an almost orthohexagonal AX5 lattice, possibly the aristotype of any 5:1 salt. [ABSTRACT FROM AUTHOR]