Christian J. Schürmann

Insertion of Cyclic Alkyl(amino) Carbene into the Si–H Bonds of Hydrochlorosilanes

Carbenes are known for their ability to abstract HCl from hydrochlorosilanes to form carbene hydrochloride adducts. In contrast, the Si-H bond insertion products RSiCl2(cAACH) (2, 4, 6, and 8) have been formed in the reaction of RSiHCl2 [R = Ar(SiMe3)N (1), Cp* (3), PhC(NtBu)2 (5), Cl (7); Ar = 2,6-iPr2C6H3] with a cyclic alkyl(amino) carbene (cAAC:) irrespective of the steric demand of the R group. The new products have been characterized by various analytical tools including X-ray crystallography, electron ionization mass spectrometry, and NMR spectroscopy. Theoretical investigations have also been performed to understand why cAAC prefers insertion into the Si-H bond rather than the dehydrohalogenation pathway.

Validation of experimental charge-density refinement strategies: when do we overfit?

A cross-validation method is supplied to judge between various strategies in multipole refinement procedures. It easily detects when the refinement of additional parameters leads to an improvement in the model or when it simply overfits the given data.

Invariom modeling of disordered structures: case studies on a dipeptide, an amino acid, and cefaclor, a cephalosporin antibiotic

Abstract Routines to facilitate the treatment of disorder in invariom modeling have been implemented in the open-source program MolecoolQt, a visualization program for charge-density work, and InvariomTool, a pre-processor program. Two published structures of an amino acid and a dipeptide and the new structure of cefaclor, a cephalosporin antibiotic, provide examples with increasing amounts of disorder, which can now be successfully modeled with invarioms. Like for ordered structures, these non-spherical scattering factors predicted by density functional theory significantly improve the structural model (figures of merit and standard deviations) also in these cases. Furthermore, they allow rapid calculation and comparison of the electrostatic potential and the molecular dipole moment for the different conformers present in the crystal structures.

Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center.

Platinum dichalcogenides have been known to exhibit two-dimensional layered structures. Herein, we describe the syntheses, isolation, and characterization of air-stable crystalline cyclic alkyl(amino) carbene (cAAC)-supported monomeric platinum disulfide three-membered ring complex [(cAAC)2 Pt(S2 )] (2). The highly reactive platinum(0) [(cAAC)2 Pt] complex (1) with two-coordinate platinum activates elemental sulfur to give 2. The brown crystals of bis-carbene platinum(II)monosulfate [(cAAC)2 Pt(SO4 )x (S2 )1-x ] (4) have been isolated when the reaction was performed in air. The dioxygen analogue of 2 was formed upon exposing the THF solution of 1 to aerial oxygen (O2 ). The binding of oxygen at the Pt(0) center was found to be reversible. Additionally, DFT study has been performed to elucidate the electronic structure and bonding scenario of 2, 3, and 4. Quantum chemical calculations showed donor-acceptor-type interaction for the Pt-S bonds in 2 and Pt-O bonds in 3 and 4.

Experimental charge density study on FLPs and a FLP reaction product

Abstract The charge density distribution of the intramolecular frustrated Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 (1), the phosphinimine HNPMes2CH2CH2B(C6F5)2 (2), as well as a FLP homologue with nitrogen NEt2CHPhCH2B(C6F5)2 (3) were investigated with Bader’s quantum theory of atoms in molecules (QTAIM). The charge densities were derived from both experimental high-resolution X-ray diffraction data (2, 3) and theoretical calculations (1, 3). The QTAIM analysis for the FLPs 1 and 3 showed the prominent B-pnictogen interaction to be weak dative bonds without significant charge-transfer. This holds also true for the B–N–bond of 2. The nitrogen atom is negatively charged, due to a charge transfer from phosphorous and shows features of a sp2-hybridization. The bond is therefore best described as a non-hypervalent Pδ+–Nδ− moiety.