Phosphinsubstituierte Chelatliganden, XXIII [1] Darstellung und NMR-Spektren von Alkyl-arylphosphinothioformamiden, R(Ph)PC(S)NHMe / Phosphine-Substituted Chelate Ligands, XXIII [1] Synthesis and NMR Spectra of Alkyl-arylphosphinothioformamides, R(Ph)PC(S)NHMe

Abstract

<jats:title>Abstract</jats:title><jats:p> A series of alkyl-arylsubstituted N-methyl phosphinothioformamides, R(Ph)PC(S)NHMe (2 a-g), with varying bulkiness of the alkyl rest was synthesized from the racemic secondary phosphines 1a-g and methyl isothiocyanate. <jats:sup>1</jats:sup>H and <jats:sup>13</jats:sup>C NMR spectra of 2a−g reveal signal sets of diastereotopic nuclei due to the asymmetry of the molecule. The chemical shift and coupling constants were confirmed by simulation in case of 2b, c. The vicinal <jats:sup>31</jats:sup>P−<jats:sup>13</jats:sup>C couplings of the menthyl and neomenthyl compounds 2f, g show an "anti-Karplus" behaviour (<jats:sup>3</jats:sup>J(gauche) &gt; <jats:sup>3</jats:sup>J(trans)) and allow the conformational assignment of the alicyclic group. The <jats:sup>31</jats:sup>P chemical shifts of 2a−d give a linear correlation with the cone angle of the alkyl substituents quoted from literature.</jats:p>

Insertion Reactions of Isothiocyanates into the Nb–P Bond of Phosphide–Niobocene Complexes

“…[10] The phosphanylthioformamides were first prepared in 1987 by the addition of diphenylphosphane across the C=N double bond of an aryl isothiocyanate. [11] Scheme 1. Formation of phosphanylthioformamide derivatives.…”