The structure and photoelectron spectra of hexa(methylimido)tetraphosphoru. evidence for three-dimensional pπ-dπ delocalization

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

“…H310BPF3 + H3uBCO it H3!1BPF3 + H3'°BCO exchange (0) 10B2H6 + "B2H6 it210B"BH6 exchange (7) However, since our objective was to establish general trends for this class of reactions rather than to obtain precise rate constants for any specific step, we postulated that H/D isotope effects introduce only small perturbations as long as the B-H and B-D bonds remain intact.3 Reactions ß and y are essentially equivalent to (8) and (9), respectively; the analogue of (a) is (4). In several cases we measured both the forward and the reverse rate constants; in most cases rate data in one direction were recorded and the reverse rate was deduced from the equilibrium constant.…”

“…6 More recently we have begun to carry out accurate structure determinations on these molecules and to try to relate the structural parameters with their photoelectron spectra. 7 We have also established that some of these cage compounds exhibit a plastic crystalline phase whereas others do not8 and we are presently examining the possible determining criteria for this behavior.…”

Aminophosphines: their chemistry and role as ligands and synthons

“…It was observed101 that only trans ‐[( i ‐Pr 2 N)PN( i ‐Pr)] 2 undergoes one electron electrochemical oxidation to produce a stable radical cation. Photoelectron spectral data for the novel cage compound, P 4 (NMe) 6 , has been reported 102. PES studies were carried out for PN 3 polycyclic rigid systems (proazaphosphatranes) and mostly ionizations pertaining to the lone pair of electrons on N and P were observed 96…”

Structure, bonding, and chemistry of closo-tetraphosphorus hexakis(methylimide), P4(NCH3)6, and its derivatives. I. The structures of the tetra-p-thio and tetra-p-oxo derivatives

“…the crystallographic 4 axis. The two sulfur atoms, S(l) and S (2) refined with the 3 °C data, are shown on the P atom only; on the other phosphorus atoms only S(2) is shown to avoid overcrowding the picture.…”

“…We have previously given a brief report on the structure and photoelectron spectrum of P4(NMe)6 itself. 2 We now present the results of a structural study of two limiting members of these series, 04P4(NMe)6 and S4P4(NMe)6. The preparations and some chemical properties of each of these have been described earlier.…”