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Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP).
The stepwise reaction mechanism leading to Na2(P2C3O4) was investigated with quantum chemical calculations and a remarkable π-delocalization was observed within the OCPCO moiety. Expand
Synthesis and characterization of terminal [Re(XCO)(CO)2(triphos)] (X=N, P): isocyanate versus phosphaethynolate complexes.
The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)(2)(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)(2)(triphos)]. The analogous isocyanatoExpand
Is the phosphaethynolate anion, (OCP)(-), an ambident nucleophile? A spectroscopic and computational study.
The reactivity of Na(OCP) was investigated towards triorganyl compounds of the heavier group 14 elements (R3EX R = Ph or (i)Pr; E = Si, Ge, Sn, Pb; X = Cl, OTf). In the case of E = Si twoExpand
Phosphaketenes as building blocks for the synthesis of triphospha heterocycles.
Heteroatom-substituted phosphaketenes, R(3) E-P=C=O (E=Si, Sn), are building blocks for silyl- and stannyl-subStituted five-membered heterocycles containing three phosphorous atoms. Expand
Cyclo-oligomerization of isocyanates with Na(PH2) or Na(OCP) as “P–” anion sources† †Electronic supplementary information (ESI) available. CCDC 1049373, 986846, 1049374, 986881 and 986854. For ESI
Na(OCP) initiates the catalytic cyclo-trimerization of isocyanates involving the mutual formation of P-heterocycles and spiro phosphoranides (shown on the right) as reactive intermediates.
Redox-triggered reversible interconversion of a monocyclic and a bicyclic phosphorus heterocycle.
Theoretical calculations suggest that phosphinidene species are involved in the rearrangement processes, and the umpolung of electronic properties from non-aromatic to highly aromatic is reversible. Expand
Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through‐Space Coupling
Significantly, 209Bi–31P through‐space coupling is observed in solid‐state 31P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction. Expand
The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study† †Electronic supplementary information (ESI) available. CCDC 986673, 1454789 and 1454790. For ESI
The phosphaethynolate anion (OCP)– has three different functions in the reaction with 2,4,6-trimethylbenzoyl chloride (MesCOCl): it acts as a nucleophile, as an en-component in [2 + 2] cycloadditionsExpand
An isolable magnesium diphosphaethynolate complex.
The reaction of magnesium chloride with two equivalents of sodium phosphaethynolate, Na[OCP]·(dioxane)2.5, yields a magnesium diphosphaeltynolate complex, [(THF)4Mg(OCP)2] (3), which was determined via a single crystal X-ray diffraction study. Expand