RESUMEN
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 amino acids, proteins, and poly(amidoamine) (PAMAM) dendrimers. Thereby, a range of new molecular and polymeric photoinitators was obtained. Real-time photo-rheology experiments demonstrated the outstanding efficiency of the PAMAM BAPOs as photoinitiators for free radical polymerization. Remarkably, it is found that PAMAM BAPOs also act as crosslinking agents to convert monofunctional methacrylate monomers into thermosetting networks without any further additives. Depending on the number of the attached BAPOs, thermosets with a different degree of crosslinking and swelling capability in water were obtained.
RESUMEN
Addition of the P-H bond in bis(mesitoyl)phosphine, HP(COMes)2 (BAPH), to a wide variety of activated carbon-carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R-P(COMes)2 , under very mild conditions in excellent yields after only a short time. All phosphines RP(COMes)2 can subsequently be oxidized to the corresponding bis(acyl)phosphane oxides, RPO(COMes)2 , a substance class belonging to the most potent photoinitiators for radical polymerizations known to date. Thus, a simple and highly atom economic method has been found that allows the preparation of a broad range of photoinitiators adapted to their specific field of application even on a large scale.
Asunto(s)
Óxidos , Fosfinas , Óxidos/química , Estereoisomerismo , Fosfinas/química , PolimerizacionRESUMEN
Phosphane, PH3 -a highly pyrophoric and toxic gas-is frequently contaminated with H2 and 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 10â wt % of PH3 . The PH3 -loaded MOF, PH3 @α-[Mg(O2 CH)2 ], is a non-pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane. α-[Mg(O2 CH)2 ] further plays a critical role in purifying PH3 from H2 and P2 H4 : at 25 °C, H2 passes through the MOF channels without adsorption, whereas PH3 adsorbs readily and only slowly desorbs under a flow of inert gas (complete desorption time≈6â h). Diphosphane, P2 H4 , is strongly adsorbed and trapped within the MOF for at least 4â months. P2 H4 @α-[Mg(O2 CH)2 ] itself is not pyrophoric and is air- and light-stable at room temperature.
RESUMEN
Reaction of the 6π-electron aromatic four-membered heterocycle (IPr)2 C2 P2 (1) (IPr=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) with [Fe2 CO9 ] gives the neutral iron tricarbonyl complex [Fe(CO)3 -η3 -{(IPr)2 C2 P2 }] (2). Oxidation with two equivalents of the ferrocenium salt, [Fe(Cp)2 ](BArF24 ), affords the dicationic tricarbonyl complex [Fe(CO)3 -η4 -{(IPr)2 C2 P2 }](BArF24 )2 (4). The one-electron oxidation proceeds under concomitant loss of one CO ligand to give the paramagnetic dicarbonyl radical cation complex [Fe(CO)2 -η4 -{(IPr)2 C2 P2 }](BArF24 ) (5). Reduction of 5 allows the preparation of the neutral dicarbonyl complex [Fe(CO)2 -η4 -{(IPr)2 C2 P2 }] (6). An analysis by various spectroscopic techniques (57 Fe Mössbauer, EPR) combined with DFT calculations gives insight into differences of the electronic structure within the members of this unique series of iron carbonyl complexes, which can be either described as electron precise or Wade-Mingos clusters.
RESUMEN
This report presents a selective synthetic approach towards borazine from ammonia borane using a dinuclear rhodium olefin homogeneous catalyst. The synthesis and spectroscopic characterization of a dirhodium ammonia borane complex as an intermediate provides insight into a possible mode of activation.
RESUMEN
Dehydrogenation of ammonia borane to well-defined products is an important but challenging reaction. A dinuclear ruthenium complex with a Ru-Ru bond bearing a diazadiene (dad) unit and olefins as non-innocent ligands catalyzes the highly selective formation of conjugated polycondensed borazine oligomers (BxNxHy), predominantly B21N21H18, the BN analogue of superbenzene.
RESUMEN
The dinuclear Ru diazadiene olefin complex, [Ru2(OTf)(µ-H)(Me2dad)(dbcot)2], is an active catalyst for hydrogen evolution in a Polymer Exchange Membrane (PEM) water electrolyser. When supported on high surface area carbon black and at 80 °C, [Ru2(OTf)(µ-H)(Me2dad)(dbcot)2]@C evolves hydrogen at the cathode of a PEM electrolysis cell (400 mA cm-2, 1.9 V). A remarkable turn over frequency (TOF) of 7800 molH2 molcatalyst -1 h-1 is maintained over 7 days of operation. A series of model reactions in homogeneous media and in electrochemical half cells, combined with DFT calculations, are used to rationalize the hydrogen evolution mechanism promoted by [Ru2(OTf)(µ-H)(Me2dad)(dbcot)2].