Di- tert -butyl(N-pyrrolyl)phosphane,-sulfide, and-selenide, studied by multinuclear magnetic resonance

 Di-tert-butyl(N-pyrrolyl)phosphane (1),-sulfide (2) and-selenide (3) were studied by 1H, 13C, 15N, 31P and 77Se NMR spectroscopy in solution. Restricted rotation about the P–N bond was observed for 1 (ΔG≠ C≈58.5 kJ/mol) and 2, 3 (ΔG≠ C≈45 kJ/mol) by 1H and 13C NMR at variable temperature. The fairly high pyrrolyl rotation barrier in 1 is ascribed to the expected steric effects exerted by the tert-butyl groups and to repulsion between the lone pairs of electrons at the phosphorus and nitrogen atoms. These repulsive forces are reduced in 2 or 3, or in di-tert-butyl(phenyl) phosphane (ΔG≠ C≈44 kJ/mol). Signs of coupling constants nJ(31P, 13C) and n+1J(31P, 1H) (n=2, 3) were determined by two-dimensional (2D) 13C/1H heteronuclear shift correlations. The preferred orientation of the pyrrolyl group in 1 is evident from the coupling constants 2J(31P, 13C(2))=+35.4 Hz and 2J(31P, 13C(5))=−9.3 Hz, typical of C(2) in syn and C(5) in anti position with respect to the assumed axis of the phosphorus lone pair. Hahn-echo extended (HEED) polarization transfer pulse sequences served for measuring 1J(31P, 15N) and isotope induced chemical shifts 1Δ15/14N(31P) from 31P NMR spectra.