Über die Lichtabsorption des zweiwertigen Kupfers in oxidischen Phasen

Ohne ZusammenfassungMit 2 Abbildungen     

Telluroselenophosphonium ions: their unusual soft-soft interactions with iodotellurate anions

Formally uncharged two-coordinate tellurium atoms in trialkyl(telluroseleno)phosphonium salts [(tBu2iPrPSeTe-p-Tol)+ (p-TolTeI2)-] () and {[(iPr3PSeTeI)+]2 (TeI6)2-} () behave as soft acceptors towards iodotellurate anions, thus exhibiting a novel type of Te...Te anion-->cation donor-acceptor interaction () and a chelating TeIV(micro-I)2TeII anion-cation coordination () in the solid state.     

Data-driven modeling and learning in science and engineering

In the past, data in which science and engineering is based, was scarce and frequently obtained by experiments proposed to verify a given hypothesis. Each experiment was able to yield only very limited data. Today, data is abundant and abundantly collected in each single experiment at a very small cost. Data-driven modeling and scientific discovery is a change of paradigm on how many problems, both in science and engineering, are addressed. Some scientific fields have been using artificial intelligence for some time due to the inherent difficulty in obtaining laws and equations to describe some phenomena. However, today data-driven approaches are also flooding fields like mechanics and materials science, where the traditional approach seemed to be highly satisfactory. In this paper we review the application of data-driven modeling and model learning procedures to different fields in science and engineering.     

Imino‐Bridged Bisphosphaalkenes (2,4‐Diphospha‐3‐azapentadienes)

Deprotonation of aminophosphaalkenes (RMe₂Si)₂C?PN(H)(R′) (R=Me, iPr; R′=tBu, 1‐adamantyl (1‐Ada), 2,4,6‐tBu₃C₆H₂ (Mes*)) followed by reactions of the corresponding Li salts Li[(RMe₂Si)₂C?P(M)(R′)] with one equivalent of the corresponding P‐chlorophosphaalkenes (RMe₂Si)₂C?PCl provides bisphosphaalkenes (2,4‐diphospha‐3‐azapentadienes) [(RMe₂Si)₂C?P]₂NR′. The thermally unstable tert‐butyliminobisphosphaalkene [(Me₃Si)₂C?P]₂NtBu ( 4 a ) undergoes isomerisation reactions by Me₃Si‐group migration that lead to mixtures of four‐membered heterocyles, but in the presence of an excess amount of (Me₃Si)₂C?PCl, 4 a furnishes an azatriphosphabicyclohexene C₃(SiMe₃)₅P₃NtBu ( 5 ) that gave red single crystals. Compound 5 contains a diphosphirane ring condensed with an azatriphospholene system that exhibits an endocylic P?C double bond and an exocyclic ylidic P⁽⁺⁾? C^(?)(SiMe₃)₂ unit. Using the bulkier iPrMe₂Si substituents at three‐coordinated carbon leads to slightly enhanced thermal stability of 2,4‐diphospha‐3‐azapentadienes [(iPrMe₂Si)₂C?P]₂NR′ (R′=tBu: 4 b ; R′=1‐Ada: 8 ). According to a low‐temperature crystal‐structure determination, 8 adopts a non‐planar structure with two distinctly differently oriented P?C sites, but ³¹P NMR spectra in solution exhibit singlet signals. ³¹P NMR spectra also reveal that bulky Mes* groups (Mes*=2,4,6‐tBu₃C₆H₂) at the central imino function lead to mixtures of symmetric and unsymmetric rotamers, thus implying hindered rotation around the P? N bonds in persistent compounds [(RMe₂Si)₂C?P]₂NMes* ( 11 a , 11 b ). DFT calculations for the parent molecule [(H₃Si)₂C?P]₂NCH₃ suggest that the non‐planar distortion of compound 8 will have steric grounds.     

Novel Properties of Iodophosphonium Ions: Kinetically Labile Behaviour and Secondary Bonding

Abstract

Neutral species R₃PX₂ in equilibria with halogenophosphonium halides R₃PX⁺X^? do not always contain hypervalent phosphorus (10-P-5)! Iodophosphonium ions R₃PI⁺ show R₃P-I… X interaction in many cases, leading to hypervalent iodine (10-I-2). Evidence for secondary IX bonds is provided by n.m.r. spectra and X-ray crystal structure determinations.