Purpose: High-intensity functional interval training (HIFT) is predominantly composed of high exercise training intensities (HiT) and loads. Both have been linked to a higher risk of overtraining and injuries in inexperienced populations. A polarized training approach is characterized by high amounts of low-intensity training (LiT) and only approximately 5%-20% HiT.
View Article and Find Full Text PDFAn additive-free manganese-catalyzed isomerization of terminal alkenes to internal alkenes is described. This reaction is implementing an inexpensive nonprecious metal catalyst. The most efficient catalyst is the borohydride complex -[Mn(dippe)(CO)(κ-BH)].
View Article and Find Full Text PDFThe room temperature reduction of various nitriles using amine boranes (ABs) catalysed by a manganese(i) alkyl complex is described. Based on experimental findings, a plausible mechanistic scenario is presented. This includes the presence of two catalytic cycles, one for productive reduction of nitriles and one for hydrogen evolution.
View Article and Find Full Text PDFA stereo- and regioselective Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The hydroboration reaction is highly -selective in the case of aryl alkynes and -selective in the case of aliphatic alkynes. The reaction requires no additives or solvents and proceeds with a catalyst loading of 1 mol % at 50-70 °C.
View Article and Find Full Text PDFBioinspired tungsten acetylene complexes containing pyridine-2-selenolato (PySe) or 6-methyl-pyridine-2-selenolato (6-MePySe) ligands were synthesized. Se NMR spectroscopy allowed for an assessment of the resonance structures in the pyridine-2-selenolato ligands and the rationalization of chemoselectivity observed in regard to 1,2 migratory insertion of HC≡CH. [W(CO)(CH)(CHCH-PySe)(PySe)] is formed exclusively via insertion of HC≡CH into the W-N bond, while the use of bulkier 6-MePySe allows for the isolation of [W(CO)(CH)(6-MePySe)], which only partially reacts with excess HC≡CH to give [W(CO)(CH)(CHCH-6-MePySe)(6-MePySe)].
View Article and Find Full Text PDFUnlabelled: The synthesis, characterization, and reactivity of several group 4 metal complexes featuring a central anionic pyrrole moiety connected via CH linkers to two phosphine donors is described. Treatment of [P(NH)P-Pr] with [MCl(THF)] (M = Zr, Hf) in the presence of base yields the dimeric complexes [M(PNP)(μ-Cl)(Cl)] featuring two bridging chloride ligands. These complexes react with sodium cyclopentadienyl and SiMeI to give the mononuclear complexes [M(PNP)(η-Cp)(Cl)] and [M(PNP)(I)], respectively.
View Article and Find Full Text PDFOlefin metathesis is one of the most significant transformations in organic chemistry and is an excellent example for efficient homogeneous catalysis. Although most currently used catalysts are primarily based on 4d and 5d metals, cycloaddition and cycloreversion reactions can also be attributed to first-row transition metals, such as Fe. Surprisingly, the potential of Mn(I)-based catalysts for olefin metathesis has been unexplored despite their prominence in homogeneous catalysis and their diagonal relationship to Ru(II).
View Article and Find Full Text PDFTesticular germ cell tumors (TGCTs) represent the most frequent malignancy in young adult men and have one the highest heritability rates among all cancers. A recent multicenter case-control study identified as the first moderate-penetrance TGCT predisposition gene. Here, we analyzed in 129 TGCT cases unselected for age of onset, histology, clinical outcome, and family history of any cancer, and the frequency of identified variants was compared to findings in 27,173 ancestry-matched cancer-free men.
View Article and Find Full Text PDFTelevision game shows have proven to be a valuable resource for studying human behavior under conditions of high stress and high stakes. However, previous work has focused mostly on choices-ignoring much of the rich visual information that is available on screen. Here, we take a first step to extracting more of this information by investigating the response times and blinking of contestants in the BBC show Mastermind.
View Article and Find Full Text PDFAlzheimer's disease (AD) is a progressive neurodegenerative disease representing the most common type of dementia in older adults. The major risk factors include increased age, genetic predisposition and socioeconomic factors. Among the genetic factors, the apolipoprotein E (ApoE) ε4 allele poses the greatest risk.
View Article and Find Full Text PDFTwo bench-stable Fe(II) alkyl complexes [Fe(κPCP-PCP-Pr)(CO)(R)] (R = CHCHCH, CH) were obtained by the treatment of [Fe(κPCP-PCP-Pr)(CO)(H)] with NaNH and subsequent addition of CHCHCHBr and CHI, respectively. The reaction proceeds via the anionic Fe(0) intermediate Na[Fe(κPCP-PCP-Pr)(CO)]. The catalytic performance of both alkyl complexes was investigated for the transfer hydrogenation of terminal and internal alkynes utilizing PhSiH and PrOH as a hydrogen source.
View Article and Find Full Text PDFUnlabelled: The synthesis, characterization, and reactivity of several new Cr(II) and Cr(III) complexes featuring an NCN pincer ligand with an arene backbone connected to amine donors NEt and NPr via CH-linkers is described. Reacting the in situ lithiated ligand precursor N(C-Br)N-Et with [CrCl(THF)] resulted in the formation of the Cr(III) complex -[Cr(κ-NCN-Et)(Cl)(THF)]. Upon reaction of lithiated N(C-Br)N-Pr with a suspension of anhydrous CrCl, the Cr(II) complex [Cr(κ-NCN-Pr)] is formed featuring two NCN ligands bound in κ-fashion.
View Article and Find Full Text PDFUnlabelled: Treatment of [Co(CO)] with the -substituted P(C-X)P ligands (X = Br, Cl; R = Pr, Bu) bearing Y = NH and CH linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [Co(PCP-R)(CO)] and [Co(PCP-R)X]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.
View Article and Find Full Text PDFThe synthesis, characterization, and reactivity of pyrrole-based Ti(III) and Ti(IV) PNP pincer complexes are described. [P(NH)P-Pr] () reacts with [TiCl(THF)] at room temperature in the presence of NEt to afford the Ti(IV) complex [Ti(PNP)(Cl)]. This complex reacts with acetone and cyclopentanone to give complexes [Ti(PNO-Pr)(Cl)] and [Ti(PNO-Pr)(Cl)], respectively.
View Article and Find Full Text PDFEfficient hydrogenations of terminal alkenes with molecular hydrogen catalyzed by well-defined bench stable Mn(I) complexes containing an N-heterocyclic carbene-based PCP pincer ligand are described. These reactions are environmentally benign and atom economic, implementing an inexpensive, earth abundant non-precious metal catalyst. A range of aromatic and aliphatic alkenes were efficiently converted into alkanes in good to excellent yields.
View Article and Find Full Text PDFIntroduction: Tissue transplantation can improve the quality of life of patients in a very wide range of applications. In 2021, around 900 people in Germany agreed to donate organs after death - the number of tissue donors was significantly higher. Nevertheless, there is a shortage of organs and tissues in Germany.
View Article and Find Full Text PDFA new pyrazole-derived PCP pincer ligand featuring a 1-methylpyrazole backbone tethered to two di(isopropyl)phosphine moieties phenylene spacers (P(CH)P-iPr) was prepared. When reacting the ligand with group six carbonyl complexes [M(CO)] (M = Cr, Mo, W) at 130 °C, complexes of the type [M(κ-PCP-iPr)(CO)] were obtained featuring a κ,-bound ligand with a pendant phosphine arm. Upon an increase of the reaction temperature to 150 °C, in the case of molybdenum, the formation of the complex [Mo(κ-PCP-iPr)(CO)] was observed featuring a weak Mo-C bond.
View Article and Find Full Text PDFSelected organometallic compounds are nowadays extensively used as highly efficient catalysts in organic synthesis. A great variety of different ligand systems exists, of which phosphine-based ligands are a significant subgroup. While mass spectrometry, predominantly electrospray ionization mass spectrometry (ESI-MS), is a standard analytical technique for the identification of new ligands and their metal complexes, there is little information on the behavior of phosphine-based ligands/molecules by electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) at low collision energies (<100 eV) in the literature.
View Article and Find Full Text PDFZ Evid Fortbild Qual Gesundhwes
September 2023
Well-defined, bench stable Mn(I) non-pincer-type complexes were tested as earth-abundant transition metal catalysts for the selective reduction of CO to boryl-protected MeOH in the presence of pinacolborane (HBpin). Essentially, quantitative yields were obtained under mild reaction conditions (1 bar CO, 60 °C), without the need of any base or additives, in the presence of the alkylcarbonyl Mn(I) bis(phosphine) complexes -[Mn(CHCHCH)(dippe)(CO)] [, dippe = 1,2-bis(diisopropylphosphino)ethane] and [Mn(dippe)(CO){(μ-H)(Bpin)}] (), that is obtained by reaction of the bench-stable precatalyst with HBpin via elimination of butanal. Preliminary mechanistic details were obtained by a combination of NMR experiments and monitoring of the catalytic reactions.
View Article and Find Full Text PDFThe synthesis of imines denotes a cornerstone in organic chemistry. The use of alcohols as renewable substituents for carbonyl-functionality represents an attractive opportunity. Consequently, carbonyl moieties can be in situ generated from alcohols upon transition-metal catalysis under inert atmosphere.
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