E–H Bond Activation of Ammonia and Water by a Geometrically Constrained Phosphorus(III) Compound

Abstract

The synthesis of ap hosphorus(III) compound bearing aN ,N-bis(3,5-di-tert-butyl-2-phenoxy)amide ligand is reported. This species has been found to react with ammonia and water,a ctivating the EÀHb onds in both substrates by formal oxidative addition to affordt he corresponding phosphorus(V) compounds.I nt he case of water,b oth O À H bonds can be activated, splitting the molecule into its constituent elements.T oo ur knowledge,t his is the first example of ac ompound based on main group elements that sequentially activates water in this manner.

Reactivity Studies on a Diazadiphosphapentalene

“…Thermalellipsoids are set at the 30 %p robability level. Selectedb ond lengths [] and angles [8]: P1ÀP1' 2.220(2), P1ÀC1' 1.820(2), P1ÀN1 1.741 (3), N1ÀC2 1.428 (3), C1ÀC2 1.341 (3);C1'-P1-N1 104.36(10), C1'-P1-P1' 87.97 (7), P1'-P1-N1 92.89 (7). solid-state molecular structure was determined by meanso fXray diffractometry,t hereby confirming the double P!BH 3 coordination ( Figure 10).…”

“…[6b] The irreversible oxidative addition to NÀHa nd OÀHb onds was also reported for Ic very recently. [7] For diphosphapentalene derivatives that possesst wo phosphorus(III) atoms at the bridgehead, [8] four major ring systems III-VI have been structurally characterized ( Figure 1b). [9][10][11][12] However,s tudies on their reactivities have been limited to the coordinationn atures towards transition metals, [8b, 11g, 12] their oxidation, [8a, 11 f, 12] and reaction with Grignardr eagents, [10a-c] and thus still remainu nexplored.…”

Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines

“…128.06 ppm). 31 2,4,6-Tri-tert-butylnitrosobenzene (2). [46] At 0°C, m-chloroperbenzoic acid (3.9 g, 2.0 equiv) in diethyl ether (25 mL) was added to 2,4,6-tert-butylaniline (3.0 g, 1.0 equiv) in diethyl ether (10 mL) and stirred overnight.…”

“…[28][29][30] Compound 1 and related species have been shown to undergo a number of addition reactions with polarized single bonds (O-H, N-H, B-H). [31][32][33] In order to probe the reactivity of 1 with respect to a selected number of polar unsaturated substrates, we report here the addition of 1 to nitrosoarenes and acylpyridines. We find evidence for a partitioning of the reaction pathway along…”

Sterically constrained tricyclic phosphine: redox behaviour, reductive and oxidative cleavage of P–C bonds, generation of a dilithium phosphaindole as a promising synthon in phosphine chemistry

“…The highly interesting chemical properties of sterically constrained bicyclic or tricyclic phosphines (1 to 3; Scheme 1) have attracted considerable attention in recent research. [1][2][3][4][5][6][7] These compounds are accessible through facile routes and have in most cases heteroatoms such as N, O, S or P bound to their central P atoms. Only recently we found facile access to the rst derivatives (3) which had the P atoms coordinated in a homoleptic fashion by three C atoms.…”