Abstract Several new nitro‐substituted adamantane compounds based on adamantane‐1,3,5,7‐tetrol were synthesized and the previously only briefly reported tetranitrate was reinvestigated. The materials completely characterized by spectroscopic methods including some X‐ray diffraction. energetic properties, thermal stabilities, sensitivities of nitrocarbamate, nitrocarbamate salt, nitrate determined compared to current composites in terms potential high‐energy dense oxidizers (HEDOs)....

Diborane(4) compounds are versatile reagents in synthetic chemistry. Generally, diboranes(4) with sp2-hybridized boron atoms react as electrophiles. By contrast, the chemistry of nucleophilic diborane(4) two sp3-hybridized is very much underdeveloped. In this work, we systematically vary substituents electron-rich bridging guanidinate substituents. way, five new diboranes synthesized and fully characterized. Using quantum chemical computations, show that electronic properties reactivity...

Phosphane, PH3 -a highly pyrophoric and toxic gas-is frequently contaminated with H2 P2 H4 , which makes its handling even more dangerous. The inexpensive metal-organic framework (MOF) magnesium formate, α-[Mg(O2 CH)2 ], can adsorb up to 10 wt % of . -loaded MOF, @α-[Mg(O2 is a non-pyrophoric, recoverable material that allows brief in air, thereby minimizing the hazards associated transport phosphane. ] further plays critical role purifying from : at 25 °C, passes through MOF channels...

The electron-rich, double-base stabilized dihydrido-diborane(4) [HB(hpp)]2 (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) combines two different, easily accessible reactive sites: the B-B and B-H bond. Herein, we report basically similar reactions of with catecholborane B-chlorocatecholborane unsuspectedly resulting in different reactivities. While reaction diborane equivalents HB(cat) proceeded formation a cationic triborane (3c2e) bond, [{HB(μ-hpp)}2 (μ-BH2 )]+ , ClB(cat) led...

Abstract Reaction of a ditriflatodiborane compound with the Lewis acids AlCl 3 or GaCl leads to abstraction two triflate substituents and dimerization resulting dicationic diborane give σ‐aromatic tetracationic tetraborane planar, rhomboid B 4 core. The exhibits four skeletal σ‐electrons involved in (3c,2e) bonds represents first stable fourfold base‐stabilized [B H ] 4+ analogue. product is isolated from reaction mixture form bright orange crystals that display fluorescence. Further...

A N-hydroxy succinimide (NHS) ester substituted bis(acyl)phosphane oxide (ACTIVE-BAPO) was prepared by phospha-Michael addition and used for an easy one-step BAPO ligation with substrates containing primary amino groups, such as acids, proteins, poly(amidoamine) (PAMAM) dendrimers. Thereby, a range of new molecular polymeric photoinitators obtained. Real-time photo-rheology experiments demonstrated the outstanding efficiency PAMAM BAPOs photoinitiators free radical polymerization....

Boron(III) cations are widely used as highly Lewis acidic reagents in synthetic chemistry. In contrast, boron(II) extremely rare and their chemistry almost completely unknown. They both acids electron donors, properties that commonly associated with catalytically active late-transition-metal complexes. This double reactivity pattern ensures a rich diverse Herein we report the facile synthesis of several new starting special diborane two easily exchangeable triflate substituents. By...

Abstract A tridentate ligand L with a P,NH,N donor motif was synthesized in few steps from commercially available precursors. Upon reaction [MnBr(CO) 5 ], an octahedral 18‐electron complex [Mn(CO) 3 ( )]Br 1 ) is obtained which adopts facial arrangement. After deprotonation of the NH group cationic unit, neutral Mn(I) amido 2 ‐ H )] formed under loss CO. Rearrangement leads to trigonal bipyramidal structure P and N centers are trans position. Further results dep‐blue anionic fragment 2H − )....

Abstract Herein reported are the reactions of an electron‐rich, Lewis acidic diborane with N‐heterocyclic aromatics to give first members unprecedented family highly charged cationic cyclophanes diboranyl units. Tetracationic 4,4‘‐bipyridine/ 1,2‐bis(4‐pyridyl)ethylene and units were synthesized their redox chemistry was studied. Cyclisation two pyrazine is accompanied by electron transfer from unit pyrazine. Our results pave way for integration redox‐active into supramolecular structures.

Cationic monoboranes are commonly associated with elusive and highly electrophilic compounds used in modern organic synthesis. By contrast, only a few cationic diboranes known their chemistry comparatively underdeveloped. This review highlights some aspects of these species reactivity focusing primarily on especially stable guanidinate‐bridged cations investigated by our group. Contrary to the intuitive presumption, sp 2 ‐hybridized discussed herein serve not exclusively as Lewis acids, but...

Abstract Addition of the P−H bond in bis(mesitoyl)phosphine, HP(COMes) 2 (BAPH), to a wide variety activated carbon–carbon double bonds as acceptors was investigated. While this phospha‐Michael addition does not proceed absence an additive or catalyst, excellent results were obtained with stoichiometric basic potassium caesium salts. Simple amine bases can be employed catalytic amounts, and tetramethylguanidine (TMG) particular is outstanding catalyst that allows preparation...

Abstract Bor(III)‐Kationen finden in der Synthesechemie eine breite Anwendung als Lewis‐Säuren. Im Gegensatz dazu sind Bor(II)‐Kationen ausgesprochen selten, und ihre Chemie ist nahezu unerforscht. Sie zugleich Lewis‐Säuren Elektronendonoren, Eigenschaften, die gewöhnlich mit katalytisch aktiven Metallkomplexen späten Übergangsmetallreihe assoziiert werden. Dieses zweifache Reaktivitätsmuster lässt reiche vielfältige erwarten. Hier berichten wir über einfache Synthese einiger neuer beginnend...

Cationic cyclophanes are widely used in a variety of applications supramolecular chemistry and materials science. In this work the authors systematically study integration electron-rich diboron units with B

The reactivity of the bis(acyl)phosphide ion [P(COR)2 ]- (BAP- , R=Ph, Mes) with silicon halides SiX4 (X=Cl, Br) and pnictogen chlorides ECl3 (E=As, Sb Bi) was investigated. reaction leads to hexacoordinate silanes SiX2 (BAP)2 in which BAP- is coordinated chelating κ2 -O,O' mode, analogously acac- . Unexpectedly, coordination behaviour differs from one interpnictogen compounds E(BAP)3 Sb) formation E-P bonds favoured over chelation via oxygen centres. Finally, BiCl3 three equivalents Na(BAP)...

Precise cell elimination within intricate cellular populations is hampered by issues arising from the multifaceted biological properties of cells and expansive reactivity chemical agents. Current platforms are often limited their complexity, toxicity, poor physical/chemical properties. Here, we report on synthesis a structurally versatile library chemically tunable bisacylphosphane oxides (BAPOs), which harnesses spatiotemporal precision light delivery, thereby establishing universal...

Abstract Die Reaktion eines Ditriflato‐Diborans mit den Lewis‐Säuren AlCl 3 oder GaCl führt zur Abspaltung beider Triflat‐Substituenten und Dimerisierung des resultierenden Diboran‐Dikations unter Bildung σ‐aromatischen, tetrakationischen Tetraborans einem planaren, rhomboiden B 4 ‐Gerüst. Verbindung weist vier σ‐Gerüstelektronen auf, die an zwei (3c,2e)‐Bindungen beteiligt sind, ist das erste stabile, vierfach basenstabilisierte [B H ] 4+ ‐Analogon. Das Produkt lässt sich aus der...

Abstract Phosphan, PH 3 – ein hochpyrophores und toxisches Gas ist gewöhnlich mit H 2 P 4 kontaminiert, was seine Handhabung gefährlich macht. Die kostengünstige metallorganische Gerüstverbindung (MOF) aus Magnesiumformiat, α‐[Mg(O CH) ], kann bis zu 10 wt % adsorbieren. Das beladene MOF, @α‐[Mg(O nicht pyrophores, rückgewinnbares Material, das eine kurze von an Luft ermöglicht die Gefahren bei der dem Transport Phosphan reduziert. ] spielt außerdem wichtige Rolle ‐Reinigung : 25 °C...

Abstract Precise cell elimination within intricate cellular populations is hampered by issues arising from the multifaceted biological properties of cells and expansive reactivity chemical agents. Current platforms are often limited their complexity, toxicity, poor physical/chemical properties. Here, we integrate spatio-temporal precision light delivery structural versatility bisacylphosphane oxides (BAPOs), establishing a universal strategy for on-demand, precise ablation in vitro vivo .