A5038250821- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Coordination Chemistry and Organometallics
- Organometallic Complex Synthesis and Catalysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Organoboron and organosilicon chemistry
- Magnetism in coordination complexes
- Inorganic Chemistry and Materials
- Inorganic Fluorides and Related Compounds
- Catalytic Cross-Coupling Reactions
- Lanthanide and Transition Metal Complexes
- Chemical Synthesis and Characterization
- Metal Extraction and Bioleaching
- Molecular Junctions and Nanostructures
- Electron Spin Resonance Studies
- Minerals Flotation and Separation Techniques
- CO2 Reduction Techniques and Catalysts
- Extraction and Separation Processes
- Semiconductor materials and devices
Friedrich-Alexander-Universität Erlangen-Nürnberg
2021-2025
In order to isolate a monometallic Mg radical, the precursor (Am)MgI⋅(CAAC) (1) was prepared (Am=tBuC(N-DIPP)
Complex [(DIPeP BDI)Ca]2 (C6 H6 ), with a C6 H62- dianion bridging two Ca2+ ions, reacts benzene to yield (biphenyl) biphenyl2- (DIPeP BDI=HC[C(Me)N-DIPeP]2 ; DIPeP=2,6-CH(Et)2 -phenyl). The biphenyl complex was also prepared by reacting ) or reduction of BDI)CaI]2 KC8 in presence biphenyl. Benzene-benzene coupling observed when the deep purple product ball-milling [(DIPP BDI)CaI(THF)]2 K/KI extracted (DIPP=2,6-CH(Me)2 -phenyl) giving crystalline BDI)Ca(THF)]2 (52 % yield). Reduction...
DFT-Calculations predict that a low-valent complex (BDI)Mg-Ca(BDI) with bulky β-diketiminate (BDI) ligands is thermodynamically stable. It was attempted to isolate such by salt-metathesis between [(DIPePBDI*)Mg-Na+]2 and [(DIPePBDI)CaI]2 (DIPePBDI = HC[C(Me)N-DIPeP]2; DIPePBDI* HC[C(tBu)N-DIPeP]2; DIPeP 2,6-CH(Et)2-phenyl). Whereas in alkane solvents no reaction observed, C6H6 led immediate C-H activation of benzene give (DIPePBDI*)MgPh (DIPePBDI)CaH, the latter crystallizing as THF-solvated...
The extremely challenging deprotonation of the amine ( t Bu 3 Si) 2 NH led to a range s-block metal complexes with superbulky N − . Depending on and solvent, can be classified as halogen-free weakly coordinating anion.
Low-valent β-diketiminate Al(I) complexes are generally synthesized in low yields (<20%). This is due to an intermolecular decomposition reaction. A new complex with a very bulky ligand DIPePBDI was obtained high yield (81%) and the raw product found be essentially pure (DIPePBDI = HC[C(Me)N(DIPeP)]2; DIPeP 2,6-C(H)Et2-phenyl). The crystal structure of (DIPePBDI)Al shows monomeric complex. reaction AlBr3 gave (DIPePBDI)AlBr2 Al(0). KCH(SiMe3)2 led deprotonation backbone Me group formation K...
Aluminyl complexes over the full series of alkali metals crystallize as dimers. The metal influences structure, dimerization energies and reactivity.
Abstract Low‐valent Mg I complexes like (BDI)Mg−Mg(BDI) have found wide‐spread application as specialty reducing agents (BDI= β ‐diketiminate). Also their redox reactivity was extensively investigated. In contrast, attempts to isolate similar Ca led reduction of the aromatic solvents or N 2 . Complex ( DIPeP BDI)Ca( μ 6 , ‐C H )Ca( BDI) VIII ) should be regarded a II complex with bridging C 2− dianion BDI=HC[C(Me)N‐DIPeP] DIPeP=2,6‐C(H)Et ‐phenyl). It can react synthon by releasing benzene...
Reaction of the AlI complex (DIPPBDI‐H)AlˉK+ with SnII (DIPPBDI)SnCl gave (DIPPBDI‐H)AlSn(DIPPBDI) (1); DIPPBDI = HC[C(Me)N(DIPP)]2, DIPP 2,6‐diisopropylphenyl, DIPPBDI‐H H2C=C(N‐DIPP)‐C(H)=C(Me)‐N‐DIPP. The crystal structure shows an asymmetric a planar but strongly distorted trigonal coordination geometry at Al and pyramidal Sn. This supports donor‐acceptor bonding model in which (DIPPBDI‐H)Alˉ donates sp2 electron pair empty p‐orbital (DIPPBDI)Sn+. Computational analysis polar covalent...
The reduction of CO 2 with low‐valent s ‐block metal complexes is limited to Mg I reducing agents. Herein, the a series CX reagents (X = O, S, N i Pr) Ca synthon [(BDI)Ca(THP)] (N ) ( VI described, which II complex that reacts like hypothetical (BDI)CaCa(BDI); BDI HC[(Me)‐N(DIPeP)] , DIPeP 2,6‐Et CH‐phenyl, THP tetrahydropyran. Reaction excess led crystallization carbonate 4 (CO 3 4+ core. stabilizing ligands also react by nucleophilic addition at backbone γ ‐C atom. only two equivalents...
Whereas the small molecule activation with b -diketiminate (BDI) Mg I complexes of type (BDI)Mg-Mg(BDI) is extensively investigated, lack similar Ca reagents prevents studies on reactivity. Herein, we report on...
The group 14 tetrel elements C, Si, Ge, Sn and Pb need to accommodate four additional electrons reach a full valence shell. However, despite fulfillment of the octet rule, tetra-anionic tetrels are highly reactive anions. considerable 4- charge on single atoms dictates their chemistry, making such anions strongly reducing, Brønsted basic or nucleophilic. Magnesium salts generally known as Zintl phases which, under forced conditions, only accessible for heavier (Mg2E, E = Si-Pb). Here we...
Abstract Reaction of [( DIPeP BDI)SrH] 2 with C 6 H 5 X (X=Cl, Br, I) led to hydride‐halogenide exchange ( BDI=HC[(Me)CN‐2,6‐(3‐pentyl)phenyl] ). Conversion rates increase increasing halogen size (F<Cl<Br<I). F was slow and ill‐defined but addition 4 gave smooth hydride‐fluoride exchange. After THF the full range Sr halogenides structurally characterized: BDI)SrX ⋅ THF] (X=F, Cl, I). Mixtures AeN“ PhSiH 3 in situ formed less defined more robust Ae metal hydride clusters (Ae x N” y z...
Abstract Reaction of a MgN“ 2 /BaN” mixture (N“=N(SiMe 3 ) with PhSiH gave three unique heterometallic Mg/Ba hydride clusters: Mg 5 Ba 4 H 11 N” 7 ⋅ (benzene) ( 1 ), 13 N“ 9 (toluene) and 12 26 ). Product formation is controlled by the ratio temperature. Crystal structures are described. While fully insoluble, clusters retain their in aromatic solvents. DFT calculations AIM analyses indicate highly ionic bonding Mg−H Ba−H bond paths. Also unusual − ⋅⋅⋅H paths observed. Catalytic...
<title>Abstract</title> The discovery of crown ether host-guest systems initiated the multidisciplinary field supramolecular chemistry. Whereas cyclic ethers selectively bind metal cations in their center, lesser known inverse crowns are rings that efficiently anionic entities. In this role, enabled spectacular multiple deprotonation reactions, often with unusual selectivity. Self-assembly around multiply charged carbanion during reaction is driving force for reactivity. Here, we report on...
Abstract In order to isolate a monometallic Mg radical, the precursor (Am)MgI⋅(CAAC) ( 1 ) was prepared (Am= t BuC(N‐DIPP) 2 , DIPP=2,6‐diisopropylphenyl, CAAC=cyclic (alkyl)(amino)carbene). Reduction of solution in toluene with reducing agent K/KI led formation deep purple complex that rapidly decomposed. Ball‐milling gave low‐valent I (Am)Mg⋅(CAAC) which after rapid extraction pentane and crystallization isolated 15 % yield. Although benzene decomposes give Mg(Am) 3 unidentified products,...
Abstract Complex [( DIPeP BDI)Ca] 2 (C 6 H ), with a C 2− dianion bridging two Ca 2+ ions, reacts benzene to yield (biphenyl) biphenyl ( BDI=HC[C(Me)N‐DIPeP] ; DIPeP=2,6‐CH(Et) ‐phenyl). The complex was also prepared by reacting ) or reduction of BDI)CaI] KC 8 in presence biphenyl. Benzene‐benzene coupling observed when the deep purple product ball‐milling DIPP BDI)CaI(THF)] K/KI extracted (DIPP=2,6‐CH(Me) ‐phenyl) giving crystalline BDI)Ca(THF)] (52 % yield). Reduction BDI)SrI] gave highly...