Ulrike Plaia

Metallkomplexe funktioneller Isocyanide, XIV [1] [3+2]-Cycloadditionen zwischen Metallo-Nitrilyliden und CS 2 und Carbenübertragung: Thiazolin-2-yliden-Komplexe von Chrom, Wolfram und Palladium / Metal Complexes of Functional Isocyanides, XIV [1] [3+2] Cycloadditions between Metallo Nitrile Ylids and CS 2 and Carbene Transfer: Thiazoline-2-ylidene Complexes of Chromium, Tungsten and Palladium

Abstract Metal-coordinated α-deprotonated ethyl isocyanoacetate reacts with carbon disulfide in a [3+2]- cycloaddition to give 1.3-thiazolin-2-ylidene complexes, the exo-sulfur function of which has been methylated and coordinated to platinum. The structure of (3) has been determined by X-ray methods. Inter alia, a surprising shortage of electron derealization in the heterocycle and strong hydrogen bonding between pairs of molecules through their NH- and CO-ester groups have been found. On reacting 3 with PdCl2(η-cyclooctadiene-1,5), carbene transfer occurs to give .

Metallkomplexe funktioneller Isocyanide, XIII Bis(oxazolidin-2-yliden)-Komplexe von Mangan(I) und Nickel(II) / Metal Complexes of Functional Isocyanides, XIII Bis(oxazolidin-2-ylidene) Complexes of Manganese(I) and Nickel(II)

Abstract The dicarbene complexes, MnBr(CO)3 [xxx] (1) and [xxx] (2), are synthesized from metal carbonyl precursors and CNCH2CH2OH . Factors influencing this 2-hydroxyalkyl isocyanide → N ,O-carbene isomerization are discussed. The crystal and molecular structure of 2 shows a distorted trigonal geometry about the central Ni atom. Extensive hydrogen bonding ((N )H ··· F 2.09, 2.38 Å ) occurs between cations and anions giving rise to infinite chains. Other pertinent bonding parameters are Ni-C (carbene) 1.860(4), 1.864(4) Å; C(carbene) [xxx] N 1.309(6), 1.304(6) Å , and C - Ni - C 97.7(2)°.