Probing cooperative effects in bimetallic clusters: indications of C-N coupling of CH4 and NH3 mediated by the cluster ion PtAu+ in the gas phase

The bimetallic cluster ion PtAu+ activates methane in the gas-phase, yielding the carbene PtAuCH2+ which further reacts with ammonia under C-N coupling. In contrast, neither Pt2+ nor Au2+ mediates C-N bond formation. This example demonstrates how bond activation in the gas phase can be tuned by cooperative effects in bimetallic clusters.     

Spectroscopic Studies of Cyclometallated Pd(II) and Pt(II) Complexes: Optical absorption and emission of single crystals of [Pd(thpy)2] and [Pt(thpy)2]

The polarized optical absorption and emission (spectra, decay times) of single crystals of [Pd(thpy)₂] and [Pt(thpy)₂] (thpy ≡ C(3′)-deprotonated form of 2-(2-thienyl)pyridine) at temperatures 1.9 K ? T ? 80 K are reported. The emission of [Pt(thpy)₂] can be influenced strongly by applied magnetic fields (0 ? H ? 6 T). Depending on the central ions Pd and Pt, the lowest excited electronic states of the single complexes are ligand-centered (LC) states and metal-to-ligand charge transfer (MLCT) states, respectively. This difference leads to distinctly dissimilar properties of the emission of both compounds. The experimental data show that the emission of single crystals of [Pd(thpy)₂] and [Pt(thpy)₂] at T ? 30 K originates from several types of traps (defect states of symmetry ³B₂?stabilized below the exciton band) with LC and MLCT character, respectively. In the Pt compound, the ³B₂ is split by spin-orbit coupling into three states. The states B and A, which determine the emission properties, are separated by Δv ～ 13 cm^?1. Both states can mix under the influence of an applied magnetic field yielding an increase of the emission intensity by a factor of ～ 1.5 at H = 6 T.     

Massenspektrometrische Untersuchung von Amiden: III—Intramolekulare Nucleophile Substitution bei der Methyl-Abspaltung aus Crotonsaurepiperidid und Vinylogen Derivaten

The methyl cleavage from piperidides of type CH₃(CH?CH)_nCONC₅H₁₀ with n = 1 to 3 does not proceed via ring contraction as shown earlier with n = 0. The fragmentation can be formulated with the concept of neighbouring group participation of the amide function which leads to a cyclic transition state. Investigations with a ²H-labelled compound in the case of n = 1 as well as energy measurements (AP, IP, E_k) agree with this assumption.     

First carbamates conversion to amides by simple alkyl group transfer from trialkylalanes

[reaction: see text] N-Monosubstituted carbamates are cleanly converted to amides under treatment with trialkylaluminum. This reaction involves an aluminum-assisted internal delivery of alkyl groups. It can be applied to new and mild protecting group strategies for alcohols.     

Synthese und Struktur von (PPh4)3[Re2NCl10]

Synthesis and Crystal Structure of (PPh₄)₃[Re₂NCl₁₀] The rhenium(V) nitrido complex (PPh₄)₃[Re₂NCl₁₀] ( 1 ) is obtained from the reaction of (PPh₄)[ReNCl₄] with 1, 3‐dioxan‐(2‐ylmethyl)diphenyl phosphine in CH₂Cl₂/CH₃CN in form of orange red crystals with the composition 1 ·2CH₂Cl₂ crystallizing in the triclinic space group P1¯ with a = 1210.7(2), b = 1232.5(1), c = 2756.3(5) pm, α = 99.68(1)°, β = 100.24(1)°, γ = 98.59(1)° and Z = 2. The crystal structure contains two symmetry independent, centrosymmetrical complex anions [Re₂NCl₁₀]^3‐ with a symmetrical nitrido bridge Re=N=Re and distances Re(1) ‐ N(1) = 181.34(5) and Re(2) ‐ N(2) = 181.51(4) pm.