Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C14H10 or anthracene), are investigated as phosphinidene sources upon thermally induced (70-90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups paramount to successful transfer; poorer π-donors give reduced no transfer. Substituent steric bulk is also implicated in Molecular beam mass spectrometry (MBMS) studies each derivative reveal derivatives be promising precursors for further...

Super-reducing excited states have the potential to activate strong bonds, leading unprecedented photoreactivity. Excited of radical anions, accessed via reduction a precatalyst followed by light absorption, been proposed drive photoredox transformations under super-reducing conditions. Here, we investigate anion naphthalene monoimide as photoreductant and find that doublet state has lifetime 24 ps, which is too short facilitate activity. To account for apparent photoreactivity anion,...

Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity centers in [Ag(bpy)

The commonly used triethylsilyl perfluoro-tetraphenylborate salt, [Et3Si+][F20-BPh4–], has been misidentified. As prepared, the cation is a hydride-bridged silane adduct [R3Si–H–SiR3+]. Under favorable circumstances it can be an effective source of triethylsilylium ion Et3Si+, but in absence stabilizing base potent electrophilicity Et3Si+ decomposes "inert" F20-BPh4– counterion.

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries, but its existence stability vivo remain controversial. We establish that HSNO is spontaneously formed high concentration when gases are mixed at room temperature the presence of metallic surfaces. Our measurements reveal by reaction + N2O3 → HNO2, where product disproportionation. These studies also suggest further with may form HNO HSSH. The length S-N...

The transannular diphosphorus bisanthracene adduct P2A2 (A = anthracene or C14H10) was synthesized from the 7-phosphadibenzonorbornadiene Me2NPA through a synthetic sequence involving chlorophosphine ClPA (28-35%) and tetracyclic salt [P2A2Cl][AlCl4] (65%) as isolated intermediates. found to transfer P2 efficiently 1,3-cyclohexadiene (CHD), 1,3-butadiene (BD), (C2H4)Pt(PPh3)2 form P2(CHD)2 (>90%), P2(BD)2 (69%), (P2)[Pt(PPh3)2]2 (47%), respectively, characterized by X-ray diffraction complex...

What is the strongest acid? Can a simple Brønsted acid be prepared that can protonate an alkane at room temperature? free of complicating effects added Lewis acids are typical common, difficult-to-handle superacid mixtures? The carborane H(CHB11 F11 ) acid. It extremely moisture-sensitive solid, by treatment anhydrous HCl with [Et3 SiHSiEt3 ][CHB11 ]. adds H2 O to form [H3 O][CHB11 ] and benzene benzenium ion salt [C6 H7 reacts butane crystalline tBu(+) n-hexane isolable hexyl carbocation...

The planarity of the second stable conformer 1,3-butadiene, archetypal diene for Diels-Alder reaction in which a planar conjugated and dienophile combine to form ring, is not established. most recent high level calculations predicted species adopt twisted, gauche structure owing steric interactions between inner terminal hydrogens rather than planar, cis favored by conjugation double bonds. cis-1,3-butadiene unambiguously confirmed experimentally indeed be with substantial dihedral angle...

Group 13 aminoxy complexes of the form (L)E(TEMPO)3 (TEMPO = 2,2,6,6-tetramethylpiperidine 1-oxyl; L THF (tetrahydrofuran) or Py (pyridine); E Al, Ga, In) were prepared and structurally characterized. The (THF)Ga(TEMPO)3 (1·THF) (Py)In(TEMPO)3 (2·Py) are shown to heterolytically cleave H2 under mild conditions (3 atm, 20 °C, t ≤ 1 h). 1·THF reacts reversibly with a formal H2-adduct that bears Ga(iii) hydride site protonated TEMPO ligand concomitant loss THF, consistent functioning as Lewis...

Proton-coupled electron transfer (PCET) underpins energy conversion processes in biological systems and fuel-forming reactions. Interrogation of the dynamics proton PCET requires tunable models, with...

Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation found proceed activation parameters ΔH(⧧) 25.5 kcal/mol ΔS(⧧) -2.43 eu accompanied formation an...

The peroxide dianion reacts with CO₂ in polar aprotic organic media to afford the hydroperoxycarbonate and carbonate radical anions. These highly reactive species, if formed lithium–O₂ cells, can lead cell degradation <italic>via</italic> oxidation of electrolyte electrode.

Significance The generation of highly reactive molecules under controlled conditions is desirable, as it allows exploration synthetic chemistry and enables spectroscopic studies such elusive species. We report here on the synthesis reactivity a precursor molecule that readily fragments with concomitant expulsion dinitrogen anthracene to release sulfur monoxide, compound interest for both chemists astrochemists.

Thermolysis of a pair dibenzo-7-phosphanorbornadiene compounds is shown to lead differing behaviors: phosphinidene sulfide release and formation amorphous P2S. These compounds, tBuP(S)A (1, A = C14H10 or anthracene; 59% isol. yield) HP(S)A (2; 63%), are available through thionation tBuPA the new secondary phosphine HPA (5), prepared from Me2NPA DIBAL-H in 50% yield. Phosphinidene [tBuP═S] transfer proceed efficiently 1 2,3-dimethyl-1,3-butadiene form Diels–Alder product 3 with zero-order...

Unlike the "parent" carborane anion CHB(11)H(11)(-), halogenated anions such as CHB(11)H(5)Br(6)(-) can be readily C-functionalized in high yield and purity, enhancing their utility weakly coordinating anions.

Dihydrogen tetrametaphosphate [P4O12H2](2-) (1) can now be synthesized and isolated as its PPN salt ([PPN](+) = [N(PPh3)2](+)) via treatment of [PPN]4[P4O12] with trifluoroacetic anhydride in wet acetone; this simple procedure affords the oxoacid 94% yield. A pKa 15.83 ± 0.11 acetonitrile was determined. reacts dehydrating agent N,N'-dicyclohexylcarbodiimide to afford [P4O11](2-) (2) 82% yield, also salt. From 2 a monohydrogen ester [P4O10(OH)(OMe)](2-) (3, 96%) derived by addition methanol,...

The reactivity of peroxide dianion O22– has been scarcely explored in organic media due to the lack soluble sources this reduced oxygen species. We now report finding that encapsulated cryptate, [O2⊂mBDCA-5t-H6]2– (1), reacts with carbon monoxide solvents at 40 °C cleanly form an carbonate. Characterization resulting hexacarboxamide carbonate cryptate by single crystal X-ray diffraction reveals forms nine complementary hydrogen bonds cryptand, [CO3⊂mBDCA-5t-H6]2– (2), a conclusion is...

A series of dibenzo-7-phosphanorbornadiene compounds, Ph3PC(R)PA (1-R; = C14H10, anthracene; R Me, Et, iPr, sBu), are reported to be capable thermal fragmentation generate alkyl-substituted phosphaalkynes (RC≡P) concomitant with triphenylphosphine and anthracene. Facile preparation these molecular precursors proceeds by treatment ClPA the appropriate ylide Ph3P═CHR (2 equiv). For methyl, ethyl, isopropyl substituents, phosphaalkyne conversions measured 56–73% in solution quantitative 31P NMR...

Targeted as an example of a compound composed carbon atom together with two stable neutral leaving groups, 7-isocyano-7-azadibenzonorbornadiene, CN2A (1, A = C14H10 or anthracene) has been synthesized and spectroscopically structurally characterized. The terminal C 1 can be transferred: mesityl nitrile oxide reacts to produce monoxide, likely via intermediacy the N-isocyanate OCN2A. Reaction [RuCl2(CO)(PCy3)2] leads [RuCl2(CO)(1)(PCy3)2] which decomposes unselectively: in product mixture,...

Metaphosphate acids cannot be thoroughly studied in aqueous media because their acidity is leveled by the solvent, and resulting metaphosphates are susceptible to acid-catalyzed hydrolysis. Exploration of metaphosphate acid chemistry has now been made possible with development a general synthetic method for organic soluble acids. Protonation [PPN]+ salts ([PPN]+ = [N(PPh3)2]+) tri-, tetra-, hexametaphosphates results five new acids, [PPN]2[P3O9H] (2), [PPN]4[(P4O12)3H8] (3),...

Abstract What is the strongest acid? Can a simple Brønsted acid be prepared that can protonate an alkane at room temperature? free of complicating effects added Lewis acids are typical common, difficult‐to‐handle superacid mixtures? The carborane H(CHB 11 F ) acid. It extremely moisture‐sensitive solid, by treatment anhydrous HCl with [Et 3 SiHSiEt ][CHB ]. adds H 2 O to form [H O][CHB ] and benzene benzenium ion salt [C 6 7 reacts butane crystalline t Bu + n ‐hexane isolable hexyl...

The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study electron transfer isolated anion. Photoinitiated (ET) between freely diffusing Ru(bpy)3(2+) and occurs with rate constant 2.0 × 10(10) M(-1) s(-1). A competing quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes 1.1 s(-1) this first-order process. driving force dependence ET pair using series derivatives allows electronic coupling reorganization...

Group 13 TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) complexes of the form (L)E(TEMPO)3 (L=THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In) were prepared and structurally characterized. The (THF)Ga(TEMPO)3 (1·THF) (Py)In(TEMPO)3 (2·Py) are shown to heterolytically cleave H2 under mild conditions (3 atm, 20 ◦C, t ≤ 1 h). 1·THF reacts reversibly with a formal H2-adduct that bears Ga(III) hydride center protonated ligand concomitant loss THF, consistent functioning as Lewis acid base,...