Platinum-mediated oxidative P–O coupling of white phosphorus and alcohols: an ab initio study

Metal-Mediated Degradation and Reaggregation of White Phosphorus

“…(6) Complex 15 marks the borderline between a simple two-electron s-type coordination of the P-P bond to a metal center and its oxidative addition to it. More distorted bicyclo-tetraphosphane-P 4 As frequently observed in metal-mediated P 4 chemistry, the reaction is not unidirectional and a variety of polymetallic-polyphosphorus ligands such as P 8 (27), P 10 (28), and P 12 (29) (see Sect. 2.2.4.3) have been isolated after chromatographic workup (Scheme 3) [38,39].…”

“…Setting up the degradation of P 4 in the presence of both transition metal complexes and suitable substrates is crucial to accomplish the direct functionalization of white phosphorus [27,28]. In many cases, the combination of P 4 with a transition metal system affords a variety of hardly predictable compounds containing unsubstituted phosphorus (P x ) ligands (x ≤ 12) in which the original tetrahedral phosphorus structure is no longer evident [3,4,[6][7][8][9][10][11][12].…”

“…Complexes of general formula [{Cp¢¢¢Co} x (P 12-n )] [x=3; n=0 (29), 4 (28), x=4, n=2 (27)] have been isolated and, for the P 8 and P 10 complexes, characterized by X-ray methods [38,39]. The related P 10 -rhodium derivative [{Cp¢¢Rh} 4 (P 10 )] (93) is also known [42].…”

Reaction of [(PPh3)3RuCl2] with white phosphorus: synthesis of the first RuII complex featuring a tetrahedro-tetraphosphorus ligand

“…The theoretical modelling of the catalytic oxidative phosphorylation of methanol with white phosphorus indicates that the formation of an η 1 -P 4 complex is a necessary prerequisite to accomplish the P-O bond-forming step. 7 The binuclear structure of 2 was confirmed by computer simulation of the eight-nuclei spin system. ‡ The proposed struc- † Synthesis of 2: an excess of white phosphorus (0.13 g, 1.09 mmol) was added to a stirred solution of 1 (0.96 g, 1.0 mmol) in dry toluene (10 ml) under nitrogen.…”