Phosphination of Carbon Monoxide: A Simple Synthesis of Sodium Phosphaethynolate (NaOCP)

Abstract

Simple basic ingredients are at the origin of the synthesis of Na(OCP), the phosphorus analogue of sodium cyanate. Na(OCP) is obtained from NaPH2 (made from Na, P, and a proton source) and CO (from carbon and air). This salt is remarkably stable, in complete contrast to HCP discovered 50 years ago.

Carbonyl migration from phosphorus to the metal in binuclear phosphaketenyl metal carbonyl complexes to give bridging diphosphido complexes

“…The linear PCO ligand with the O atom linking to the Mn atom is a three-electron donor to give the Mn atom a 16-electron configuration. The triplet state Mn(CO) 3 (PCO) structure 13-1T, lying 10.5 kcal mol À1 (B3LYP) or 23.2 kcal mol À1 (BP86) in energy above 13-1S, has approximately square planar Mn coordination and a bent P-bonded 2 . Three singlet structures 28-1S, 28-2S, and 28-3S were found having energies within 20 kcal mol À1 ( Fig.…”

“…3 Our results, reported in this paper, predict the generation of isomeric phosphide and diphosphide Mn 2 (CO) n+2 P 2 complexes having six to nine terminal CO groups in the unsaturated Mn 2 (CO) n (PCO) 2 (n = 7, 6, 5) systems. In addition, Mn 2 (CO) 6 (PCO) 2 structures containing three-electron donor bridging Z 2 -m-PCO groups have been discovered. Such structures are plausible intermediates in the migration of CO from phosphorus in a PCO ligand to a metal atom.…”

From a Phosphaketenyl‐Functionalized Germylene to 1,3‐Digerma‐2,4‐diphosphacyclobutadiene

“…[1,2] After the successful synthesis of an isolable Si=Pc ompound reported by Bickelhaupt and co-worker in 1984, [3] several striking examples featuring multiply bonded heavier Group 14 and 15 elements have been isolated and structurally characterized. [1][2][3][4][5] However,the synthesis of more unsaturated triply bonded REP(E= Si, Ge) species remains challenging because of the even higher tendency of EPbonds to undergo dimerization or oligomerization.Recently,w hen we attempted to synthesize as table SiÀP triply bonded compound, aphosphasilyne [LSi P],wecould only isolate its corresponding head-to-tail dimer,t he 4p-electron resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene.[4k] Herein, we wish to report the unexpectedly facile access to the first head-to-tail dimer of ap hosphagermyne,s tarting from an ovel phosphaketenyl-functionalized germylene.F urthermore,a nu nprecedented N,P-heterocyclic bis-germylene could be synthesized via ar emarkable and unexpected condensation reaction.At first, the N-heterocyclic [6] were allowed to react with one molar equivalent of sodium phosphaethynolate,ac onvenient anionic phosphorus atom transfer reagent for which as ynthesis was recently developed, [7] to give the phosphaketenyl germylenes 2a and 2b,r espectively,i n quantitative yield according to 1 Hand 31 PNMR spectroscopy (Scheme 1). Both were isolated as yellow crystals in 90 and 92 %y ields,r espectively.T heir constitutions and compositions were proved by 1 H, 13 C, 31 PNMR spectroscopy,e lemental analyses and high resolution-mass spectrometry (HR-MS) (see the Supporting Information).…”

The 2‐Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes

“…[1] Following this seminal report, several additional synthetic routes to this species have been documented, thus allowing for the bulk preparation of alkali metal salts of the anion in high yields. [2][3][4][5][6] In the last five years,this species has gone from being ac hemical curiosity to av ersatile chemical precursor for ar ange of phosphorus-containing compounds, including heterocycles, [5][6][7][8][9][10] low-valent compounds, [10,11] and novel phosphines. [12][13][14] Thec oordination chemistry of the anion to d-block and f-block metals has also been explored.…”