Synthesis of 4-Diarylamino-3-iodo-2(5H)-furanones via the Simultaneous α-Iodination and N β -Arylation by an Efficient Difunctionalizable Transfer Reagent PhI(OAc)2

During the studies on the intramolecular cyclization of 4-arylamino-2(5H)-furanones via the Pd-catalyzed C-H activation, a kind of difunctionalization reaction caused by the designed oxidant PhI(OAc)₂ [(diacetoxyiodo)benzene, DIB] was accidentally discovered. When 1.5 eq. DIB is used as a difunctionalizable transfer reagent in the 40 h reaction at 60°C and CH₃CN as solvent, 4-diarylamino-3-iodo-2(5H)-furanones can be obtained with the yields of 57–91% (usually more than 73%). The simultaneous α-iodination and N ^β -arylation reaction without metal catalyst is efficient and convenient. This novel utilization with a greater atom economy provides a simple and practical conversion route for the synthesis of the potential biological 2(5H)-furanone compounds containing multifunctional groups.     

Fluorescent Indolo[3,2-a]phenazines against Toxoplasma gondii: Concise Synthesis by Gold-Catalyzed Cycloisomerization with 1,2-Silyl Migration and ipso-Iodination Suzuki Sequence

A gold-catalyzed cycloisomerization of 2-indolyl-3-[(trimethylsilyl)ethynyl)]quinoxalines with concomitant 1,2-silyl shift forms 6-(trimethylsilyl)indolo[3,2-a]phenazines in moderate to excellent yield. These silylated heterocycles are readily transformed into 6-aryl-indolo[3,2-a]phenazines in moderate to good yield by one-pot ipso-iodination Suzuki coupling. The title compounds represent a novel type of tunable luminophore. Structure-property relationships for 6-aryl-indolo[3,2-a]phenazines obtained from Hammett correlations with σ_p+ substituent parameters indicate that emission maxima, Stokes shifts, and fluorescence quantum yields can be fine-tuned by the remote para-aryl substituent. Furthermore, indolo[3,2-a]phenazines were found to exhibit interesting activities against medically relevant pathogens such as the Apicomplexa parasite Toxoplasma gondii with an IC₅₀ of up to 0.67±0.13 μM. Thus, these compounds are promising candidates for novel anti-parasitic therapies.     

Aerobic oxidative α-iodination of carbonyl compounds using molecular iodine activated by a nitrate-based catalytic system

The novel reaction system comprising air/NH₄NO_3(cat.)/I₂/H₂SO_4(cat.) is introduced as a simple, safe, cheap, efficient, and regioselective mediator for direct aerobic oxidative α-iodination of aryl, heteroaryl, alkyl, and cycloalkyl methyl ketones. The reaction system enabled the moderate to quantitative regioselective iodination of a large range of different methyl ketone derivatives including those bearing oxidizable heteroatom (S, N) substituents. Several activated aromatic compounds were also efficiently and selectively iodinated. The practical applicability of the presented reaction system was shown on 20 mmol scale under ambient pressure and 100% conversion of substrate was achieved.     

Mass spectral evidence for the conversion of benzenephosphonic acid to its cyclic,trimeric anhydride and of benzenephosphonous acid to phenylphosphine

The mass spectra of benzenephosphonic and benzenephosphonous acids are readily observable under normal operating conditions and, at low sample temperatures (50 to 85°C), the 70 eV electron-impact degradations are characteristic. The phosphonic acid shows peaks for the molecular ion at 158 amu and for characteristic degradation fragments at 141 (C₆H₅PO₂H), 94 (C₆H₆O), 78 to 7 (C₆H₆, C₆H₅), 65 (H₃PO₂, C₅H₅), 51 (C4_H3), 47 (PO) and 39 (C3_H3) amu. Above 120°, however, and after a pressure surge indicative of a thermal dehydration in the sample, a peak at 420 amu associated with the cyclic, trimeric anhydride, (C6_H5PO2)₃, is observed along with a characteristic set of fragment peaks at 373, 357, 343, 327, 280, 262, 233, 216 and 199 amu, whose interrelations are summarized in Scheme 1. The phosphonous acid, at 75°C and at 70 eV, shows peaks for the molecular ion at 142 amu and for characteristic degradation fragments at 124 (C6_H5PO), 111 to 107 (C6_H5PH ± 2H), 94 (C6_H6O), 78 to 7 (C6_H6, C6_H5), 65 (H3_PO2, C5_H5), 51 (C4_H3), 47 (PO) and 39 (C3_H3) amu. The phenylphosphine is apparently formed by rearrangement in the excited state after electron-impact rather than by thermal disproportionation in the sample as the latter requires the formation of relatively more of the phosphonic acid than is observed. At higher sample temperatures (120°C) somewhat increased amounts of the phosphonic acid, presumably formed by partial disproportionation in the sample, are observed. Accurate mass assignments and broad metastables confirm the postulated fragmentation processes.     

Syntheses and vibrational spectra of xenon(VI) fluorozirconate(IV) and xenon(VI) fluorohafnate(IV)

Liquid xenon difluoride at 140°C does not react with zirconium or hafnium tetrafluorides, neither does liquid xenon hexafluoride at 60°C. Therefore reactions between the corresponding hydrazinium fluorometalates or ammonium fluorometalates and xenon difluoride and xenon hexafluoride, respectively, were carried out. N₂H₆ZrF₆ and N₂H₆HfF₆ react with xenon difluoride at 60°C again yielding only the corresponding tetrafluorides, while the analogous reaction with (NH₄)₂ZrF₆ and (NH₄)₂HfF₆ proceeds at 170°C yielding the corresponding ammonium pentafluorometalates, which are stable and do not react further with excessive xenon difluoride up to 200°C.The reaction between N₂H₆ZrF₆ or N₂H₆HfF₆ and xenon hexafluoride proceeds at room temperature yielding a series of thermally unstable compounds of the type mXeF₆.MF₄ (M = Zr, Hf) where m ? 6. The final products which are stable at room temperature are XeF₆.MF₄ (M = Zr,Hf). Spectroscopic evidence suggests that these compounds are salts of a XeF⁺₅ cation squashed between a polymeric anion of the type (MF₅)^x-_x.     

The structure of R-NiF3, and synthesis,and magnetism of new R3 MIINiIVF6 (M = Fe,Co, Cu,Zn), and MIINiIIF4 (M = Co,Cu)

Neutron diffraction, at 2 K, of R-NiF₃ indicates the formulation approaches Ni^IINi^IVF₆, with Ni^II − F = 1.959(3) and Ni^IV − F = 1.811(3) Å, but 295 K data allow for only a slight increase in any Ni^III. Relatives have been precipitated from liquid anhydrous HF, at ≤ 20 °C, by adding K₂NiF₆ to M(SbF₆)₂ (M = Co, Cu, Zn) or M(AsF₆)₂ (M = Fe). CuNiF₆ like NiNiF₆ is metastable and loses F₂ easily, above 40 °C. CuNiF₆ is reduced by Xe or C₃F₆ at −20 °C; CoNiF₆ by H₂ at 350 °C, each giving pseudo-rutile MNiF₄. Magnetic data indicate the dominant formulation is M^IINi^IVF₆ (Ni(IV) low spin d⁶) with field dependence in CoNiF₆ (≤ 220 K) and FeNiF₆ (≤ 295 K).     

Efficient oxidative resolution of a P-stereogenic triarylphosphine and asymmetric synthesis of a P-stereogenic atropoisomeric biphenyl diphosphine dioxide

Racemic 3-methoxyphenyl(1-naphthyl)phenylphosphine 1 was effectively resolved via an oxidative resolution procedure utilizing l-menthyl bromoacetate as the resolving agent to give enantiopure 3-methoxyphenyl(1-naphthyl)phenylphosphine oxide (R)-2 in 41% yield. Reduction of the resolved (R)-4 with HSiCl₃/NEt₃ provided the corresponding phosphine (R)-1 in >97% ee. Ortho-iodination of the enantiopure (R)-4 followed by Ullmann coupling of the resulting iodoarylphosphine oxide gave a P-stereogenic and atropoisomeric biphenyl diphosphine dioxide as a single diastereoisomer. The latter transformation constitutes the first example of an effective transfer of a P-centered chirality to an axial chirality of the atropoisomeric biaryl system. The absolute configurations of the resolved phosphine and the atropoisomeric biaryl system have also been established.     

Polymorphie von SrTa2O6

Polymorphism of SrTa₂O₆ Orthorhombic SrTa₂O₆ is a new low temperature modification related to orthorhombic CaTa₂O₆. SrTa₂O₆(orh.) was obtained when the wellknown modification SrTa₂O₆(TTB) which is related to the tetragonal tungsten bronzes was heated in the presence of a transporting agent (chlorine) or a mineralizer (melt of B₂O₃) at temperatures below 1150°C. It could be prepared by the reaction of a 1:1 mixture of Sr(NO₃)₂ or SrCO₃ with Ta₂O₅ in a sealed quartz glass tube as well. SrTa₂O₆(orh.) also occurred as an intermediate phase of the reaction of the corresponding 1:2 mixture at temperatures below 900°C (e. g. 840°C). Indexing of Guinier powder patterns led to the following unit cell: a = 11.006 Å, b = 7.638 Å, c = 5.622 Å. At temperatures above 1220°C SrTa₂O₆(orh.) changes (in air) to SrTa₂O₆(TTB). A reversal of this transition could not be achieved without the presence of a mineralizer or a transporting agent. Ca_xSr_1?xTa₂O₆ solid solutions of the low temperature form could not definitely be established. However, at 1300°C solid TTB solutions of Ca_xSr_1?xTa₂O₆ were formed. For x > 0.05 the TTB unit cells are orthorhombically distorted. For x ≥ 0.85 the x-ray powder patterns of the solid solutions looked like the one of CaTa₂O₆(orh.) and no TTB-structure was observed at 1300°C.     

Syntheses and vibrational spectra of xenon(VI) fluorogallate,xenon(VI) fluoroaluminate and xenon(VI) fluoroindate

Liquid xenon difluoride at 140°C does not react with aluminium, gallium, and indium trifluorides, neither does liquid xenon hexafluoride at 60°C. Therefore the reactions between the corresponding hydrazinium fluorometalates (N₂H₆AlF₅, N₂H₆GaF₅ and N₂H₅InF₄) and XeF₂ and XeF₆ were carried out. N₂H₆AlF₅, N₂H₆GaF₅ and N₂H₅InF₄ react with XeF₂ at 60°C (at 25°C in the case of indium) yielding only the corresponding trifluorides, while the reaction with XeF₆ proceeds at room temperature (at - 25°C in the case of indium) yielding XeF₆.2AlF₃, XeF₆.GaF₃ and xenon(VI) fluoroindate(III) contaminated with indium trifluoride. Spectroscopic evidence suggests that these compounds are salts of the XeF⁺₅ cation squashed between polymeric anions of the type (M₂F₇)^x-_x or (MF₄)^x-_x.     

Iodine-mediated direct synthesis of 3-iodoflavones

Molecular iodine has been used for the regioselective, one pot, direct synthesis of 3-iodoflavones from 2′-allyloxy chalcones, 2′-hydroxy chalcones and flavones. Allyl deprotection, cyclization dehydrogenation and α-iodination of 2′-allyloxychalcones has been achieved in a single step to offer 3-iodoflavones.     

Über Kondensierte Phosphate des Melamins

Condensed Phosphates of Melamine The title compounds with the formulae (C₃H₆N₆)_n · H_n+2P_nO_3n+1 (linear phosphates, n = 2; 3) and (C₃H₆N₆ · HOP₃)_m (cyclic phosphates, m = 3; 4; 6; 8 and high polymeric phosphate) are obtained as crystalline hydrates by interaction of the corresponding sodium phosphates with stoichiometric amounts of melamine hydrochloride and hydrochloric acid or melamine hydrochloride in aqueous solution. With the exception of (C₃H₆N₆ · HPO₃)₄ · 6H₂O ( I ) these hydrates decompose at ～100°C forming a mixture of mono and diphosphate which transforms at ～200°C into pure melamine diphosphate and at ～250°C into melamine polyphosphate. In contrast to this I froms at ～100°C the anhydrous melamine tetrametaphosphate which converts at ～150°C into melamine polyphosphate. Melamine diphosphate and polyphosphate are also formed on heating melamine monophosphate C₃H₆N₆ · H₃PO₄.     

Oxydations et halogénations régiosélectives et réactions carbéniques de dérivés de sucres portant un groupement thioéther

Regioselective Oxidations, Regioselective Halogenations and Carbene Reactions of Sugar Derivatives Bearing a Thioether Group Regioselective stoechiometrically controlled procedures are described for the oxidation of thiosugars either at the sulfur atom (to sulfoxides or sulfones) or at a hydroxymethylene group (to ketosugars). Ruthenium tetraoxide reacted at both sites. Chloration (SO₂Cl₂) of β-ketothioether sugar derivative 3 took place exclusively at C(6). Evidence is given that a chlorosulfonium intermediate C was formed when the dichloroketothiosugar derivative 6 was treated with SO₂Cl₂. The carbene generated from the tosylhydrazone 16 rearranged to the enoses 17–20 , the migrating group coming in equal proportions from C(4) and C(6). Some stereochemical aspects of these reactions are discussed.     

Pechini synthesis and characterization of molybdenum carbide and nickel molybdenum carbide

Carbides, such as η-Ni₆Mo₆C, are considered as low-cost substitutes for noble metal catalysts for present applications in hydrodesulfurization and for a possible future sulfur-tolerant fuel cell anode catalyst. Most synthesis methods set the carbon content of the carbides by a carbon-based atmosphere or solid carbon in the synthesis. We show here that β-Mo₂C and η-Ni₆Mo₆C can be synthesized using a Pechini process, simply by heating metal acetates mixed with citric acid and ethylene glycol in one step under H₂ with the only source of carbon being the precursor solution. The β-Mo₂C forms when heating a Mo-acetate precursor at 850 °C. When using Ni- and Mo-acetates, β-Mo₂C forms at 700 °C and lower temperatures, while η-Ni₆Mo₆C forms during heating at 800-900 °C. The η-Ni₆Mo₆C has a surface area of 95.5 m² g⁻¹ and less than 10 m² g⁻¹ when prepared at 800 and 900 °C, respectively. Some Ni₃C, Ni, and NiC impurities are also present in the nanostructured η-Ni₆Mo₆C that was prepared at 900 °C. The η-Ni₆Mo₆C materials made by the Pechini process are compared with those made from a traditional synthesis, using metal organic precursors at 1000 °C under CO/CO₂ mixtures with a carbon activity of 0.011. Our results imply that H₂ and the Pechini process can be used to achieve carbon activities similar to those obtained by methods using gaseous or solid carbon sources.     

三水合希土氯化物(镨、钆)与18－冠－6配合物的热化学研究

制备了ＲＥＣｌ３．３Ｈ２Ｏ（ＲＥ＝Ｐｒ，Ｇｄ）与１８Ｃ６的固态配合物，其化学组成为：ＲＥＣｌ３，１８Ｃ６．３Ｈ２Ｏ。对其进行了ＩＲ，溶解度、ＤＴＧ和ＴＧ分析，推测了热分解机理，测量了２９８．１５Ｋ时１８Ｃ６及两种配合物在无水乙醇中的积分，及ＲＥＣｌ３，３Ｈ２Ｏ在１８Ｃ６－Ｃ２Ｈ２ＯＨ溶液中的溶解配位热效应，依据本文所设计的热化学循环，求得了ＲＥＣｌ３，３Ｈ２Ｏ（ｓ）与１８Ｃ６（ｓ）生成ＲＥＣｌ３，     

Regioselectivity of the 1,3‐Oxathiolane Formation in the Lewis Acid‐Catalyzed Reaction of Thioketones with Asymmetrically Substituted Oxiranes

The reactions of the aromatic thioketone 4,4′‐dimethoxythiobenzophenone ( 1 ) with three monosubstituted oxiranes 3a – c in the presence of BF₃⋅Et₂O or SnCl₄ in dry CH₂Cl₂ led to the corresponding 1 : 1 adducts, i.e., 1,3‐oxathiolanes 4a – b with R at C(5) and 8c with Ph at C(4). In addition, 1,3‐dioxolanes 7a and 7c , and the unexpected 1 : 2 adducts 6a – b were obtained (Scheme 2 and Table 1). In the case of the aliphatic, nonenolizable thioketone 1,1,3,3‐tetramethylindane‐2‐thione ( 2 ) and 3a – c with BF₃⋅Et₂O as catalyst, only 1 : 1 adducts, i.e. 1,3‐oxathiolanes 10a – b with R at C(5) and 11a – c with R or Ph at C(4), were formed (Scheme 6 and Table 2). In control experiments, the 1 : 1 adducts 4a and 4b were treated with 2‐methyloxirane ( 3a ) in the presence of BF₃⋅Et₂O to yield the 1 : 2 adduct 6a and 1 : 1 : 1 adduct 9 , respectively (Scheme 5). The structures of 6a , 8c , 10a , 11a , and 11c were confirmed by X‐ray crystallography (Figs. 1 – 5). The results described in the present paper show that alkyl and aryl substituents have significant influence upon the regioselectivity in the process of the ring opening of the complexed oxirane by the nucleophilic attack of the thiocarbonyl S‐atom: the preferred nucleophilic attack occurs at C(3) of alkyl‐substituted oxiranes (O−C(3) cleavage) but at C(2) of phenyloxirane (O−C(2) cleavage).     

Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand

Two ruthenium acetylide complexes [Ru]?C≡C?C≡C?C(OR)(C₃H₅)₂ ( 2 , R=H and 2 a , R=CH₃; [Ru]=Cp(PPh₃)₂Ru) each with two cyclopropyl rings were synthesized from TMS?C≡C?C≡C?C(OH)(C₃H₅)₂ ( 1 ; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF₆ afforded the vinylidene complexes 3 and 3 a , respectively. When NH₄PF₆ was used, instead of KPF₆, additional ring‐opening reaction took place on one of the three‐membered ring. Treatment of [Ru]Cl with 1,3‐butadiyne ( 6 ), bearing an epoxide ring, afforded acetylide complex 7 with a furyl ring. Treatment of 2 a with Ph₃CPF₆ presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C₃H₅)₂}[PF₆] ( 10 ), which was not isolated. Additions of various alcohols in a solution of 10 generated a number of disubstituted allenylidene complexes {[Ru]=C=C=C(OR)?C=C(C₃H₅)₂}[PF₆] ( 11 ). Treatment of 11 with K₂CO₃ afforded the acetylide complex 12 bearing a carbonyl group, characterized by single X‐ray diffraction analysis. Addition of a primary amine to 10 caused cleavage of the farthermost C=C bond and several allenylidene complexes {[Ru]=C=C=C(Me)(NHR)}[PF₆] ( 18 ) were isolated.     

Carbon Participation in the Solvolysis of Tertiary Norbornyl Derivatives Norbornanes. Part 15. 6-substituted 2-methylnorbornyl 2-exo- and 2-endo-2,4-dinitrophenyl ethers

The solvolysis rates and products of the tertiary 2-methyl-2-exo- and -2-endo-norbornyl 2,4-dinitrophenyl ethers 1 and 2 , (X = 2,4-(NO₂)₂₂C₆H₃O) have been determined. The different sensitivities of the rates of these ethers to the inductive effect of substituents at C(6) indicate that graded bridging of C(2) by C(6) occurs in the ionization of the exo-ethers 1 , not, however, in the ionization of the endo-ethers 2. In both cases hydrolysis leads to 2-methyl-2-exo-norbornanols only. Consequently, substitution takes place with retention at C(2) in the exo-series 1 and with inversion at C(2) in the endo-series 2. It is concluded that stereoelectronic and polar effects, rather than steric bulk effects, determine the high exo/endo rate ratios of the parent norbornyl derivatives 1a and 2a .     

Structure and Reactivity of Xanthocorrinoids. Part III. The first example of a pinacol-type rearrangement in the corrin series

The transformation of the c-acetic-acid chain of hexamethyl Coα, Coβ-dicyanocobyrinate into an ethyl group (→ 2 ) as well as the synthesis of the pentadecaalkyl-cobalticorrin 6d from commercial cyanocobalamin are described. On reaction of 2 or 6d with O₂ in the presence of ascorbic acid, migration of the CH₃ group at C(5) to the vicinal position C(6) takes place concomitantly with the introduction of a carbonyl group at C(5).     

Further Evidence for ‘Extended’ Cumulene Complexes: Derivatives from Reactions with Halide Anions and Water

Reactions of [Ru{C=C(H)-1,4-C₆H₄C≡CH}(PPh₃)₂Cp]BF₄ ([ 1 a ]BF₄) with hydrohalic acids, HX, results in the formation of [Ru{C≡C-1,4-C₆H₄-C(X)=CH₂}(PPh₃)₂Cp] [X=Cl ( 2 a-Cl ), Br ( 2 a-Br )], arising from facile Markovnikov addition of halide anions to the putative quinoidal cumulene cation [Ru(=C=C=C₆H₄=C=CH₂)(PPh₃)₂Cp]⁺. Similarly, [M{C=C(H)-1,4-C₆H₄-C≡CH}(LL)Cp ]BF₄ [M(LL)Cp’=Ru(PPh₃)₂Cp ([ 1 a ]BF₄); Ru(dppe)Cp* ([ 1 b ]BF₄); Fe(dppe)Cp ([ 1 c ]BF₄); Fe(dppe)Cp* ([ 1 d ]BF₄)] react with H⁺/H₂O to give the acyl-functionalised phenylacetylide complexes [M{C≡C-1,4-C₆H₄-C(=O)CH₃}(LL)Cp’] ( 3 a – d ) after workup. The Markovnikov addition of the nucleophile to the remote alkyne in the cations [ 1 a–d ]⁺ is difficult to rationalise from the vinylidene form of the precursor and is much more satisfactorily explained from initial isomerisation to the quinoidal cumulene complexes [M(=C=C=C₆H₄=C=CH₂)(LL)Cp’]⁺ prior to attack at the more exposed, remote quaternary carbon. Thus, whilst representative acetylide complexes [Ru(C≡C-1,4-C₆H₄-C≡CH)(PPh₃)₂Cp] ( 4 a ) and [Ru(C≡C-1,4-C₆H₄-C≡CH)(dppe)Cp*] ( 4 b ) reacted with the relatively small electrophiles [CN]⁺ and [C₇H₇]⁺ at the β-carbon to give the expected vinylidene complexes, the bulky trityl ([CPh₃]⁺) electrophile reacted with [M(C≡C-1,4-C₆H₄-C≡CH)(LL)Cp’] [M(LL)Cp’=Ru(PPh₃)₂Cp ( 4 a ); Ru(dppe)Cp* ( 4 b ); Fe(dppe)Cp ( 4 c ); Fe(dppe)Cp* ( 4 d )] at the more exposed remote end of the carbon-rich ligand to give the putative quinoidal cumulene complexes [M{C=C=C₆H₄=C=C(H)CPh₃}(LL)Cp’]⁺, which were isolated as the water adducts [M{C≡C-1,4-C₆H₄-C(=O)CH₂CPh₃}(LL)Cp’] ( 6 a–d ). Evincing the scope of the formation of such extended cumulenes from ethynyl-substituted arylvinylene precursors, the rather reactive half-sandwich (5-ethynyl-2-thienyl)vinylidene complexes [M{C=C(H)-2,5-^cC₄H₂S-C≡CH}(LL)Cp’]BF₄ ([ 7 a – d ]BF₄ add water readily to give [M{C≡C-2,5-^cC₄H₂S-C(=O)CH₃}(LL)Cp’] ( 8 a – d )].     

Frustrated Lewis Pair Chemistry Derived from Bulky Allenyl and Propargyl Phosphanes

The dimesitylpropargylphosphanes mes₂P?CH₂?C≡C?R 6 a (R=H), 6 b (R=CH₃), 6 c (R=SiMe₃) and the allene mes₂P?C(CH₃)=C=CH₂ ( 8 ) were reacted with Piers’ borane, HB(C₆F₅)₂. Compound 6 a gave mes₂PCH₂CH=CH(B(C₆F₅)₂] ( 9 a ). In contrast, addition of HB(C₆F₅)₂ to 6 b and 6 c gave mixtures of 9 b (R=CH₃) and 9 c (R=SiMe₃) with the regioisomers mes₂P?CH₂?C[B(C₆F₅)₂]=CRH 2 b (R=CH₃) and 2 c (R=SiMe₃), respectively. Compounds 2 b , c underwent rapid phosphane/borane (P/B) frustrated Lewis pair (FLP) reactions under mild conditions. Compound 2 c reacted with nitric oxide (NO) to give the persistent FLP NO radical 11 . The systems 2 b , c cleaved dihydrogen at room temperature to give the respective phosphonium/hydridoborate products 13 b , c . Compound 13 c transferred the H⁺/H^? pair to a small series of enamines. Compound 13 c was also a metal‐free catalyst (5 mol %) for the hydrogenation of the enamines. The allene 8 reacted with B(C₆F₅)₃ to give the zwitterionic phosphonium/borate 17 . The ‐PPh₂‐substituted mes₂P‐propargyl system 6 d underwent a typical 1,2‐P/B‐addition reaction to the C≡C triple bond to form the phosphetium/borate zwitterion 20 . Several products were characterized by X‐ray diffraction.