Diphosphanylmetallocenes of Main-Group Elements.
Ontology highlight
ABSTRACT:
SUBMITTER: Muller C
PROVIDER: S-EPMC8252418 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:A series of di- and polymetal complexes involving closed-shell, heavy main-group atoms and ions shows a selection of special physical properties. These involve short metal-metal contacts, low entropies of formation and, most interestingly, strong Raman bands at low wavenumbers. These results together with the constitution of the coordination compounds, where the majority of electrons are assembled on the highly polarizable metal atoms and ions, experimental results have been interpreted in terms of direct, partial covalent metal-metal bonding. Previous theoretical studies have challenged this view and instead attributed the obvious attractive forces involved to secondary-type of interactions, such as dispersion. This study utilizes a multitude of theoretical tools, such as natural bond order (NBO) and natural energy decomposition analysis (NEDA), non-covalent interaction (NCI) analysis, electron localization functions (ELFs), and atoms-in-molecules (AIM) to characterize the interactions in models comprising closed-shell dimers, as well as experimentally studied ring and cage systems constituting the main reason for the hypotheses on metal-metal interactions. The results show that all experimental results can be attributed to the covalent interactions between the electron-rich, metal centers and the bridging anions in ring and cage coordination compounds of high symmetry, where the experimentally observed effects can be traced to the combination of covalent interactions between the metal centers and the anions along the edges of the ring and cage systems in combination with the cooperative effects generated by the high symmetry of these ring and cage systems.
| S-EPMC9825979 | biostudies-literature
Project description:Heterobimetallic cationic sandwich complexes [M(μ-Cp)M'Cp]+ of group 13 (M=Ga, In) and group 14 (M'=Ge, Sn) elements have been prepared as [WCA]- salts (WCA=Al(ORF )4 ; ORF =OC(CF3 )3 ). Their molecular structures include free apical gallium or indium atoms. The sandwich complexes were formed in the reactions of [M(HMB)]+ [WCA]- (HMB=C6 Me6 ) with the free metallocenes [M'Cp2 ]. Their structures are related to known stannocene and stannocenium salts; the unprecedented germanium analogues, namely the free germanocenium cation [GeCp]+ and the corresponding triple-decker complex cation [CpGe(μ-Cp)GeCp]+ , are described herein. By variation of the reaction conditions, these sandwich complexes can be transformed into the group 13/14 mixed cationic coordination polymer [{In(HMB)(μ-SnCp2 )}n ][WCA]n . This polymeric chain motif was also successfully replicated by the synthesis of complexes [{Ga/In(HMB)(μ-FeCp2 )}n ][WCA]n containing FeCp2 as a bridging ligand.
| S-EPMC7702131 | biostudies-literature
Project description:We present herein an in-depth study of complexes in which a molecule containing a boron-boron triple bond is bound to tellurate cations. The analysis allows the description of these salts as true ? complexes between the B-B triple bond and the tellurium center. These complexes thus extend the well-known Dewar-Chatt-Duncanson model of bonding to compounds made up solely of p block elements. Structural, spectroscopic and computational evidence is offered to argue that a set of recently reported heterocycles consisting of phenyltellurium cations complexed to diborynes bear all the hallmarks of ?-complexes in the ?-complex/metallacycle continuum envisioned by Joseph Chatt. Described as such, these compounds are unique in representing the extreme of a metal-free continuum with conventional unsaturated three-membered rings (cyclopropenes, azirenes, borirenes) occupying the opposite end.
| S-EPMC7317709 | biostudies-literature
Project description:The efficient catalytic reduction of imines with phenylsilane is achieved by using the potassium, calcium and strontium based catalysts [(DMAT)K?(THF)]? , (DMAT)2 Ca?(THF)2 and (DMAT)2 Sr?(THF)2 (DMAT=2-dimethylamino-?-trimethylsilylbenzyl). Eight different aldimines and the ketimine Ph2 C=NPh could be successfully reduced by PhSiH3 at temperatures between 25-60?°C with catalyst loadings down to 2.5?mol?%. Also, simple amides like KN(SiMe3 )2 or Ae[N(SiMe3 )2 ]2 (Ae=Ca, Sr, Ba) catalyze this reaction. Activities increase with metal size. For most substrates the activity increases along the row K<Ca<Sr<Ba. Fastest conversion was found for imines with alkyl substituents at N and aryl rings at C, for example, PhC(H)=NtBu, while tBuC(H)=NtBu or PhC(H)=NPh react much slower. Reasonable functional group tolerance is observed. The proposed metal hydride mechanism is supported by stoichiometric reactions using a catalyst model system, isolation of intermediates and DFT calculations.
| S-EPMC6973166 | biostudies-literature
Project description:The reduction of carbon dioxide (CO2) is of interest to the chemical industry, as many synthetic materials can be derived from CO2. To help determine the reagents needed for the functionalization of carbon dioxide this experimental and computational study describes the reduction of CO2 to formate and CO with hydride, electron, and proton sources in the presence of sterically bulky Lewis acids and bases. The insertion of carbon dioxide into a main group hydride, generating a main group formate, was computed to be more thermodynamically favorable for more hydridic (reducing) main group hydrides. A ten kcal/mol increase in hydricity (more reducing) of a main group hydride resulted in a 35% increase in the main group hydride's ability to insert CO2 into the main group hydride bond. The resulting main group formate exhibited a hydricity (reducing ability) about 10% less than the respective main group hydride prior to CO2 insertion. Coordination of a second identical Lewis acid to a main group formate complex further reduced the hydricity by about another 20%. The addition of electrons to the CO adduct of t Bu3P and B(C6F5)3 resulted in converting the sequestered CO2 molecule to CO. Reduction of the CO2 adduct of t Bu3P and B(C6F5)3 with both electrons and protons resulted in only proton reduction.
| S-EPMC6440204 | biostudies-literature
Project description:The reactions of group 14 tetrafluorides (SiF4, GeF4, and SnF4) and group 15 pentafluorides (PF5, AsF5, and SbF5) with the CAAC-based trifluoride reagent [MeCAACH][F(HF)2] led to the isolation of salts containing discrete 5- or 6-coordinated fluoroanions. The syntheses of [MeCAACH][SiF5], [MeCAACH][GeF5], [MeCAACH][(THF)SnF5], and the structurally related [MeCAACH][(dioxane)SnF5], [MeCAACH][PF6], [MeCAACH][AsF6], and [MeCAACH][SbF6] are effective, selective and in high yield. All compounds were characterized by X-ray single-crystal structure analysis, NMR and Raman spectroscopy. It is worth noting that the synthesized [MeCAACH][GeF5] is a rare example of a structurally characterized compound with discrete [GeF5]- anion, while [MeCAACH][(THF)SnF5] and [MeCAACH][(dioxane)SnF5] represent the first compounds with discrete octahedrally coordinated tin fluoride anions with incorporated solvent molecules. Finally, the aldiminium-based cation [MeCAACH]+ proved to be suitable for the stabilization of rare discrete main group fluoride anions.
| S-EPMC10489094 | biostudies-literature
Project description:Density functional theory calculations using the PBE0-D3BJ hybrid functional have been employed to investigate the complexation of main-group metal-cations with [2.2.2]paracyclophane and deltaphane. Geometry optimization under symmetry constraints was performed to observe the mode of coordination that a metal-cation adopts when it resides inside the cyclophane cavity. Thermodynamic properties were investigated to note the trends of stability along a group of metals. To further investigate the bonding properties, Morokuma-Ziegler energy decomposition analysis, natural bond orbital analysis and Bader's analysis were employed. It was observed that most of the main-group metal complexes with cyclophanes prefer an η6η6η6 coordination mode where the metal-cation sits in the centre of the cyclophane cavity. There is an increased thermodynamic stability in [2.2.2]paracyclophane complexes compared to their deltaphane analogues while the reverse is true regarding the strength of coordination based on interaction energy.
| S-EPMC9056411 | biostudies-literature
Project description:The duality of group II introns, capable of carrying out both self-splicing and retromobility reactions, is hypothesized to have played a profound role in the evolution of eukaryotes. These introns likely provided the framework for the emergence of eukaryotic retroelements, spliceosomal introns and other key components of the spliceosome. Group II introns are found in all three domains of life and are therefore considered to be exceptionally successful mobile genetic elements. Initially identified in organellar genomes, group II introns are found in bacteria, chloroplasts, and mitochondria of plants and fungi, but not in nuclear genomes. Although there is no doubt that prokaryotic and organellar group II introns are evolutionary related, there are remarkable differences in survival strategies between them. Furthermore, an evolutionary relationship of group II introns to eukaryotic retroelements, including telomeres, and spliceosomes is unmistakable.
| S-EPMC5659887 | biostudies-literature
Project description:The ISCR elements ISCR3, ISCR4, ISCR5, ISCR14, and ISCR16 all share a percent G+C of 68 to 69%. They also share between 75% and 97% identity in their transposase open reading frames. Furthermore, with the exception of ISCR5, they are all found adjacent to sections of groEL that display the highest identity to the same gene from Xanthomonas spp. The combined information is consistent with the descent from an ancestral ISCR element in a Xanthomonas-like organism.
| S-EPMC2565877 | biostudies-literature
Project description:Polycomb group genes (PcG) encode a group of about 16 proteins that were first identified in Drosophila as repressors of homeotic genes. PcG proteins are present in all metazoans and are best characterized as transcriptional repressors. In Drosophila, these proteins are known as epigenetic regulators because they remember, but do not establish, the patterned expression state of homeotic genes throughout development. PcG proteins, in general, are not DNA binding proteins, but act in protein complexes to repress transcription at specific target genes. How are PcG proteins recruited to the DNA? In Drosophila, there are specific regulatory DNA elements called Polycomb group response elements (PREs) that bring PcG protein complexes to the DNA. Drosophila PREs are made up of binding sites for a complex array of DNA binding proteins. Functional PRE assays in transgenes have shown that PREs act in the context of other regulatory DNA and PRE activity is highly dependent on genomic context. Drosophila PREs tend to regulate genes with a complex array of regulatory DNA in a cell or tissue-specific fashion and it is the interplay between regulatory DNA that dictates PRE function. In mammals, PcG proteins are more diverse and there are multiple ways to recruit PcG complexes, including RNA-mediated recruitment. In this review, we discuss evidence for PREs in vertebrates and explore similarities and differences between Drosophila and vertebrate PREs.
| S-EPMC4157523 | biostudies-literature