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1.
Eur J Trauma Emerg Surg ; 49(2): 607-617, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36792724

ABSTRACT

PURPOSE: The threat of terror is omnipresent in Europe and the number of attacks worldwide is increasing. The target of attacks in Europe is usually the civilian population. Incalculable dangerous situations at the scene of the event and severe injury patterns such as complex gunshot and explosion injuries with a high number of highly life-threatening people present rescue forces, emergency physicians and subsequently hospitals with medical, organizational as well as tactical and strategic challenges. The Terror and Disaster Surgical Care (TDSC®) course trains clinical decision-makers to meet these challenges of a TerrorMASCAL in the first 24-48 h. METHODS: A table-top exercise was developed for the TDSC® course as a decision training tool, which was prospectively evaluated in six courses. The evaluation took place in 3 courses of the version 1.0, in 3 courses in the further developed version 2.0 to different target values like, e.g., the accuracy of the in-hospital triage. Furthermore, 16 TDSC® course instructors were evaluated. RESULTS: For the evaluation, n = 360 patient charts for version 1.0 and n = 369 for version 2.0 could be evaluated. Overall, the table-top exercise was found to be suitable for training of internal clinical decision makers. Version 2.0 was also able to depict the action and decision-making paths in a stable and valid manner compared to the previous version 1.0. The evaluation of the instructors also confirmed the further value and improvement of version 2.0. CONCLUSION: With this prospective study, the table-top exercise of the TDSC® course was tested for decision stability and consistency of the participants' decision paths. This could be proven for the selected target variables, it further showed an improvement of the training situation. A further development of the table-top exercise, in particular also using digital modules, will allow a further optimization. http://www.bundeswehrkrankenhaus-ulm.de.


Subject(s)
Disaster Planning , Disasters , Wounds, Gunshot , Humans , Prospective Studies , Triage , Wounds, Gunshot/surgery
2.
Chem Sci ; 13(26): 7907-7913, 2022 Jul 06.
Article in English | MEDLINE | ID: mdl-35865905

ABSTRACT

Imidyl and nitrene metal species play an important role in the N-functionalisation of unreactive C-H bonds as well as the aziridination of olefines. We report on the synthesis of the trigonal imido iron complexes [Fe(NMes)L2]0,- (L = -N{Dipp}SiMe3); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl) via reaction of mesityl azide (MesN3) with the linear iron precursors [FeL2]0,-. UV-vis-, EPR-, 57Fe Mössbauer spectroscopy, magnetometry, and computational methods suggest for the reduced form an electronic structure as a ferromagnetically coupled iron(ii) imidyl radical, whereas oxidation leads to mixed iron(iii) imidyl and electrophilic iron(ii) nitrene character. Reactivity studies show that both complexes are capable of H atom abstraction from C-H bonds. Further, the reduced form [Fe(NMes)L2]- reacts nucleophilically with CS2 by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L2] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.

3.
Inorg Chem ; 61(20): 7794-7803, 2022 May 23.
Article in English | MEDLINE | ID: mdl-35522526

ABSTRACT

In this report, we present intricate pathways for the synthesis of linear nickel(I) silylamide K{m}[Ni(NR2)2] (NR2 = -N(SiMe3)2). This is achieved first via the reduction of nickel(II) trisamide Li(donor)4[Ni(NR2)3] (Li(thf)x[1]) with KC8 in the presence of 18-crown-6 or crypt.222. In due course, the behavior of Li(donor)4[Ni(NR2)3] as a source of masked two-coordinate nickel(II) hexamethyldisilazanide is explored, leading to the formation of nickel(I) and nickel(II) N-donor adducts, as well as metal-metal-bonded dinickel(I) trisamide K(toluene)[Ni2(NR2)3] (K(toluene)[5]). Finally, a convenient and reliable synthesis of K{m}[Ni(NR2)2] by ligand exchange of phosphines in [Ni(NR2)(PPh3)2] with K{m}(NR2) is presented. This allows for the comprehensive analysis of its electronic properties which reveals a fluxional behavior in solution with tight anion/cation interactions.

4.
Angew Chem Int Ed Engl ; 60(28): 15376-15380, 2021 Jul 05.
Article in English | MEDLINE | ID: mdl-33977634

ABSTRACT

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L2 ]- , (L=N(Dipp)SiMe3 ), Dipp=2,6-diisopropylphenyl) with very long Co-NAryl bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X-Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes. Computational analyses corroborate these findings and further reveal that the high-spin state is responsible for the imidyl character. Exchange of the Dipp substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me3 Si shift from the ancillary ligand set to the imidyl nitrogen, revealing a highly reactive, nucleophilic character of the imidyl unit.

5.
Angew Chem Int Ed Engl ; 59(22): 8527-8531, 2020 May 25.
Article in English | MEDLINE | ID: mdl-32119164

ABSTRACT

The 3d-metal mediated nitrene transfer is under intense scrutiny due to its potential as an atom economic and ecologically benign way for the directed amination of (un)functionalised C-H bonds. Here we present the isolation and characterisation of a rare, trigonal imido cobalt(III) complex, which bears a rather long cobalt-imido bond. It can cleanly cleave strong C-H bonds with a bond dissociation energy of up to 92 kcal mol-1 in an intermolecular fashion, unprecedented for imido cobalt complexes. This resulted in the amido cobalt(II) complex [Co(hmds)2 (NHt Bu)]- . Kinetic studies on this reaction revealed an H atom transfer mechanism. Remarkably, the cobalt(II) amide itself is capable of mediating H atom abstraction or stepwise proton/electron transfer depending on the substrate. A cobalt-mediated catalytic application for substrate dehydrogenation using an organo azide is presented.

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