The title compound, [Os(3)(C(25)H(22)As(2))(CO)(10)], contains a triangle of singly bonded Os atoms; both arsine ligands are equatorial with respect to the Os(3) triangle. Each arsine-substituted Os atom bears one equatorial and two axial terminal carbonyl ligands, whereas the unsubstituted Os atom bears two equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings in the diphenyl-arsino groups are 67.42 (16) and 61.99 (16)°. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds into zigzag chains propagating along [010].
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http://dx.doi.org/10.1107/S1600536812024208 | DOI Listing |
J Chem Phys
November 2024
Department of Materials Science and Engineering, Saarland University, 66123 Saarbrücken, Germany.
The split-charge equilibration method is extended to describe dissipative charge transfer similarly as the Drude model, whereby the complex-valued frequency-dependent dielectric permittivities or conductivities of dielectrics and metals can be mimicked at non-zero frequencies. To demonstrate its feasibility, a resistor-capacitor circuit is simulated using an all-atom representation for the resistor and capacitor. The dynamics reproduce the expected charging process and Nyquist noise, the latter resulting from the thermal voltages acting on individual split charges.
View Article and Find Full Text PDFNat Commun
August 2024
Shanghai key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Frontiers Science Center of Drug Target Identification and Delivery, School of Pharmaceutical Sciences, Shanghai Jiao Tong University, Shanghai, China.
Site-selective C(sp)-H arylation is an appealing strategy to synthesize complex arene structures but remains a challenge facing synthetic chemists. Here we report the use of photoredox-mediated hydrogen atom transfer (HAT) catalysis to accomplish the site-selective α-C(sp)-H arylation of dialkylamine-derived ureas through 1,4-radical aryl migration, by which a wide array of benzylamine motifs can be incorporated to the medicinally relevant systems in the late-stage installation steps. In contrast to previous efforts, this C-H arylation protocol exhibits specific site-selectivity, proforming predominantly on sterically more-hindered secondary and tertiary α-amino carbon centers, while the C-H functionalization of sterically less-hindered N-methyl group can be effectively circumvented in most cases.
View Article and Find Full Text PDFJ Chem Theory Comput
July 2024
Computational and Chemical Biology, Fondazione Istituto Italiano di Tecnologia, Via Morego 30, Genoa 16163, Italy.
Estimating the potential energy of a molecular system at a quantum level of theory is a task of paramount importance in computational chemistry. The often employed density functional theory approach allows one to accomplish this task, yet most often at significant computational costs. This prompted the community to develop so-called machine learning potentials to achieve near-quantum accuracy at molecular mechanics computational cost.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Department of Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, California 95064, United States.
Phosphine oxides and arsine oxides are common laboratory reagents with diverse applications that stem from the chemistry exhibited by these monomeric species. Stibine oxides are, in contrast, generally dimeric or oligomeric species because of the reactivity-quenching self-association of the highly polarized stiboryl (Sb=O/Sb-O) group. We recently isolated DippSbO (Dipp = 2,6-diisopropylphenyl), the first example of a kinetically stabilized monomeric stibine oxide, which exists as a bench-stable solid and bears an unperturbed stiboryl group.
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