Oxyphosphoranes with an oxaphospholene ring: analysis of the activation barriers of the isomerization process

Tin–carbon bond formation by simple addition of cyclic dienes to a bis(amino)stannylene: a mechanistic study

“…The higher value for 5 seems to come from the bulkier indenyl ligand. Besides this intramolecular reorientation, a second fluxional behaviour can be found in solutions of 5 which arises from flipping of the tin atom between the two carbon atoms C ( 11) and C(13), as may be deduced from 'H [coalescence of proton signals at C(11) and C ( 13)] or 13C NMR spectra (equivalence at > 263 or > 283 K for carbon atoms within the six-membered ring). Comparable 1,3 shifts of trimethyltin in the indenyl compound have been previously reported. '…”

A computational study of the activation of allenoates by Lewis bases and the reactivity of intermediate adducts

“…The assumption of electrostatic P⋯O interactions is supported by the 35 P, 13 C and 1 H NMR spectra which indicate a trigonal bipyramidal coordinated phosphorous atom and a short P⋯O distance in the PPh 2 OMe•H 2 CvCvCHCOMe adduct. 66 Furthermore, no E-type transition state (no direct P⋯O interactions) is found for the addition of Pbu to 1. However, the E-type transition states are localized in the case of Pph and Hmpt, probably due to the steric effect by the phenyl groups and −NMe 2 groups.…”

Synthesis, structure, and reaction of tricoordinate stibine and tetracoordinate stiboranide

“…The relative preference of substituent occupying the apical site is particularly known as apicophilicity [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36]. From many experimental systems and theoretical calculations, an oxygen atom is determined to be much more apicophilic than a carbon atom [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36]. Antiapicophilic compound, which violates relative apicophilicity of the elements, generally has high energy and is unstable, thus easily isomerizes into its stable apicophilic compound.…”