B−B Bond Nucleophilicity in a Tetraaryl μ-Hydridodiborane(4) Anion

The tetraaryl μ-hydridodiborane(4) anion [ 2 H]⁻ possesses nucleophilic B−B and B−H bonds. Treatment of K[ 2 H] with the electrophilic 9-H-9-borafluorene (HBFlu) furnishes the B₃ cluster K[ 3 ], with a triangular boron core linked through two BHB two-electron, three-center bonds and one electron-precise B−B bond, reminiscent of the prominent [B₃H₈]⁻ anion. Upon heating or prolonged stirring at room temperature, K[ 3 ] rearranges to a slightly more stable isomer K[ 3 a ]. The reaction of M[ 2 H] (M⁺=Li⁺, K⁺) with MeI or Me₃SiCl leads to equimolar amounts of 9-R-9-borafluorene and HBFlu (R=Me or Me₃Si). Thus, [ 2 H]⁻ behaves as a masked [:BFlu]⁻ nucleophile. The HBFlu by-product was used in situ to establish a tandem substitution-hydroboration reaction: a 1:1 mixture of M[ 2 H] and allyl bromide gave the 1,3-propylene-linked ditopic 9-borafluorene 5 as sole product. M[ 2 H] also participates in unprecedented [4+1] cycloadditions with dienes to furnish dialkyl diaryl spiroborates, M[R₂BFlu].     

Self-trapping of magnetic oscillation modes in Landau flux-closure structures

We investigated the magnetodynamics in rectangular Permalloy platelets by means of time-resolved x-ray photoemission microscopy. 10 nm thick platelets of size 16 x 32 microm were excited by an oscillatory field along the short side of the sample with a fundamental frequency of 500 MHz and considerable contributions of higher harmonics. Under the influence of the oscillatory field, the Néel wall in the initial classical Landau pattern shifts away from the center, corresponding to an induced magnetic moment perpendicular to the exciting field. This phenomenon is explained by a self-trapping effect of the dominating spin-wave mode when the system is excited just below the resonance frequency. The basic driving mechanism is the maximization of entropy.     

Complexes of mixed silicon halides with 4‐picoline

The reaction products of an addition reaction of five different silicon tetrahalides with the aromatic nitro­gen base 4‐methyl­pyridine are presented. The following five structures are isomorphous: (I) tetra­chloro­bis(4‐methyl­pyridine)­silicon, C₁₂H₁₄­Cl₄­N₂Si, (II) bromo­tri­chloro­bis(4‐methyl­pyridine)­silicon, C₁₂H₁₄­Br­Cl₃N₂Si, (III) di­bromo­di­chloro­bis(4‐methyl­pyridine)­silicon, C₁₂H₁₄­Br₂­Cl₂N₂Si, (IV) tri­bromo­chloro­bis(4‐methyl­pyridine)­silicon, C₁₂H₁₄Br₃­Cl­N₂Si, and (V) tetra­bromo­bis(4‐methyl­pyridine)­silicon, C₁₂H₁₄Br₄N₂Si. The mol­ecules of (I) and (V), with D_2h symmetry, have crystallographic C_2h symmetry, while the molecules of (II), (III) and (IV) have a lower molecular symmetry, but as a result of the disorder of the halogen ligands, they appear to be of the same crystallographic symmetry. The environment around the Si atom can be described as a slightly distorted octahedron with the methyl­pyridine ligands occupying axial positions and the four halogen ligands in the equatorial plane. In spite of the different substitution pattern of the silicon centre, there are only insignificant differences between these five structures.     

Synthesis,Characterization and Crystal Structure of Some Novel 1‐Aryl‐2‐Thioxo‐2,3‐Dihydro‐1H‐Quinazolin‐4‐Ones

The base catalyzed intramolecular nucleophilic cyclization of 1‐(2‐haloaroyl)‐3‐aryl thioureas ( 1a‐i ), in the presence of DMF afforded the 1‐aryl‐2‐thioxo‐2,3‐dihydro‐1H‐quinazolin‐4‐ones ( 2a‐i ). The structures were confirmed by spectroscopic data, elemental analyses and in case of the 2c by single crystal X‐ray diffraction data. The mechanistic studies support an intramolecular nucleophilic substitution (S_NAr mechanism) rather than intramolecular aromatic substitution (S_RN1 mechanism).     

Solvent-dependent formation of two different Cd(II) complexes with p-BrC6H4C(S)NHP(O)(OiPr)2 (HL). Crystallographic modification of Cd(HL)2L2

Reaction of the potassium salt of N-(diisopropoxyphosphoryl)-p-bromothiobenzamide p-BrC₆H₄C(S)NHP(O)(OiPr)₂ (HL) with Cd(II) cations in freshly dried and distilled EtOH leads exclusively to the complex [Cd(p-BrC₆H₄C(S)NH₂-S)(L-O,S)₂] ([Cd(L^I)L₂]), while the same reaction in H₂O leads to the complex [Cd(HL-O)₂(L-O,S)₂] ([Cd(HL)₂L₂]). The corresponding reactions with Zn(II) always lead to the complex [Zn(L-O,S)₂] ([ZnL₂]) regardless of the solvent. The crystal structure of [Cd(HL)₂L₂]^.2/3H₂O reveals to be a polymorph to the previously reported anhydrous [Cd(HL)₂L₂].