- Program finansujący:
- Narodowe Centrum Nauki (NCN) (National Science Centre)
- UMO-2016/21/B/ST5/03088 z dnia 2017-07-19
- Okres realizacji:
- 2017-07-19 - 2020-07-18
- Kierownik projektu:
- dr hab. inż. Rafał Grubba
- Członkowie zespołu:
- Realizowany w:
- Katedra Chemii Nieorganicznej
- Wartość projektu:
- 466 500.00 PLN
- Typ zgłoszenia:
- Krajowy Program Badawczy
- Projekt krajowy
- Politechnika Gdańska
Publikacje powiązane z tym projektem
Diphosphinoboranes as Intramolecular Frustrated Lewis Pairs: P–B–P Bond Systems for the Activation of Dihydrogen, Carbon Dioxide, and Phenyl IsocyanatePublikacja
Herein, we present the first example of the activation of small molecules by P-B-P bond systems. The reactivity study involves reactions of two selected diphosphinoboranes, (tBu2P)2BPh (1’) and (Cy2P)2BNiPr2 (2), that differ in terms of their structural and electronic properties for the activation of dihydrogen, carbon dioxide, and phenyl isocyanate. Diphosphinoborane 1’ activates H2 under very mild conditions in the absence of...
Activation of N2O and SO2 by the P–B Bond System. Reversible Binding of SO2 by the P–O–B Geminal Frustrated Lewis PairPublikacja
Herein, we present the first transformation of borylphosphine into borylphosphinite using nitrous oxide. Borylphosphine reacts with N2O via insertion of a single oxygen atom into the P−B bond and formation of a P−O−B bond system. Borylphosphine and borylphosphinite capture SO2 and activate it in an irreversible and reversible manner, respectively.
The monomeric diaminophosphinoboranes readily react with CO2 under mild conditions to cleanly form products of the general formula R2P-C(=O)-O-B(NR2)2 in the absence of a catalyst. The isolated products from the CO2-phosphinoboration were fully characterized by NMR spectroscopy, IR spectroscopy, and X-ray diffraction. The mechanism of CO2 phosphinoboration with diaminophosphinoboranes was elucidated by DFT calculations.
Diphosphination of CO2 and CS2 mediated by frustrated Lewis pairs - catalytic route to phosphanyl derivatives of formic and dithioformic acidPublikacja
The first example of CO2 diphosphination is described. Reactions of unsymmetrical diphosphanes with CE2 (E = O, S) catalyzed by BPh3 insert a CE2 molecule into the P-P bond with formation of the products of the general formula R2P-E-C(=E)-PR2. The obtained CO2 adducts arise from synergistic interaction of diphosphane and borane with CO2 molecule.
We present a series of amino- and aryl(diphosphino)boranes R2PB(R’’)PR’2, where R2P, R’2P = tBu2P, tBuPhP, Ph2P, Cy2P, and R’’ = iPr2N, Ph, which were obtained via the metathesis reaction of iPr2NBBr2 or PhBBr2 with selected lithium phosphides. The structures of isolated diphosphinoboranes were characterized in the solid state and in solution by means of X-ray diffraction and NMR spectroscopy, respectively. The utility of these...
Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, 31 P NMR Spectra, and ReactivitiesPublikacja
Theoretical studies of the bonding interactions and most important properties are carried out for isolable phosphanylphosphinidene complexes of transition metals. Three main types of phosphanylphosphinidene complexes are distinguished, based on the way in which the phosphanylphosphinidene ligand bonds to the metal center: (i) side-on complexes of platinum, where the R2Pβ–Pα ligand mimics structural features of free singlet phosphanylphosphinidenes...
We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via salt metathesis reactionof halophosphanes with metal phosphides in high yield. We vastly expanded...
Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β-Diketiminato LigandPublikacja
We report the synthesis of the first series of terminal phosphido iron complexes supported by a β‐diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono‐ or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl2Li(dme)2] with the R2PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and...
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