Theoretical study of structural patterns in CH2OP2 isomers

Abstract

DFT calculations have been performed on the derivatives of formula CH 2 OP 2 to determine their total energy, the relative energy between the isomers and their geometry. Among compounds with a P-C-P linkage, the most stable one is the 2-hydroxy-1,2-diphosphirene II.1, a threemembered heterocycle with a P=C unsaturation. The phosphavinylidene(oxo)phosphorane HP=C=P(O)H IV.5 (which has the same skeleton as the experimentally obtained Mes*P=C=P(O)Mes*) lies 36.30 kcal mol -1 above it. The least stable compounds are carbenes; the singlet carbenes are more stable than the triplet ones.

Quantum Chemical Calculations on CHOP Derivatives—Spanning the Chemical Space of Phosphinidenes, Phosphaketenes, Oxaphosphirenes, and COP− Isomers

“…Somewhat similar is the situation for strained ring systems containing phosphorus for which phosphiranes ( IV ) and 1 H -phosphirenes ( V ) [5] may serve as good cases in point. An existing synthetic challenge is represented by oxaphosphiranes ( VI ) [6,7], only experimentally described as a ligand in transition metal complexes, being valuable due to a high potential in polymer chemistry, and oxaphosphirenes ( VII ) [8,9] (a 3-phosphinyl-1 H -oxaphosphirene was computed as one of the possible CHOP isomers [10]) for which not even a (failed) attempt exists in the literature; the latter may stem from a (discouraging) degree of antiaromaticity [11]. The first stable derivative of a phosphaketene, possessing the general formula RP=C=O, was reported by Appel (R = Mes* = 2,4,6-tri- tert -butylphenyl) [12,13], and which remained the only derivative for a long time.…”

In silico modelling of chelate stabilized tetrylene derivatives

“…The molecular structures of model PCPX ligands were optimized at the DFT (PBE0/Def2-TZVP) level of theory, with their most relevant geometrical parameters being presented in Table S1. † It must be recalled that the structural properties of model compounds containing the P]C-P]O fragment have already been described in previous DFT studies by our group [23][24][25] and therefore, a detailed structural characterization of the PCPO models employed herein is beyond the purposes of the current study. However, theoretical data reported for derivatives incorporating the P]C-P]S moiety are scarce.…”

Theoretical Investigation on the PCP(O) Linear Moiety: How to Stabilize Diphosphaallenic Derivatives

“…8 Owing to our interest in diphosphaallenes containing the P C P( E) unit (E = O, S), 4 we have recently theoretically investigated all the possible isomers with the formula H 2 CP 2 O, including the 1,3-diphosphaallene model compound HP C P( O)H. 9 This study suggested that although the isomers containing the P C P O moiety do not have the lowest relative energy, their stabilization might be achieved by varying the substituents at the phosphorus atoms.…”