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A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (-), have been formed via molecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (RP-BF-N; -) and involve the release of dinitrogen (N), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (P to P). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds. Compounds - are blue emissive in the solution and solid states with absolute quantum yields (Φ) ranging from 12 to 68%.
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Mono- and Bis-Phosphine Promoted Incorporation of Boron, Nitrogen, and Phosphorus into Heterocycles via Staudinger Reactions of Borafluorene Azides.
Inorg Chem
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Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 18-596, Cambridge, Massachusetts 02139-4307, United States.
We report the synthesis and characterization of a series of BNP-incorporated borafluorenate heterocycles formed via thermolysis reactions of pyridylphosphine and bis(phosphine)-coordinated borafluorene azides. The use of diphenyl-2-pyridylphosphine (PyPhP), trans-1,2-bis(diphenylphosphino)ethylene (PhP(H)C═C(H)PPh), and bis(diphenylphosphino)methane (PhPC(H)PPh) as stabilizing ligands resulted in Staudinger reactions to form complex heterocycles with four- (BNP, BNPC, PN) and five-membered (BNPC and BNPC) rings, which were successfully isolated and fully characterized by multinuclear NMR and X-ray crystallography. However, when bis(diphenylphosphino)benzene (PhP-Ph-PPh) was used as the ligand in a reaction with 9-bromo-9-borafluorene (BF-Br), due to the close proximity of the donor P atoms, the diphosphine-stabilized borafluoronium ion with an unusual borafluorene dibromide anion was formed.
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Acc Chem Res
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Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 18-596, Cambridge, Massachusetts 02139-4307, United States.
ConspectusBoron heterocycles represent an important subset of heteroatom-incorporated rings, attracting attention from organic, inorganic, and materials chemists. The empty p orbital at the boron center makes them stand out as quintessential Lewis acidic molecules, also serving as a means to modulate electronic structure and photophysical properties in a facile manner. As boracycles are ripe for extensive functionalization, they are used in catalysis, chemical biology, materials science, and continue to be explored as chemical synthons for conjugated materials and reagents.
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Inorg Chem
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Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 18-596, Cambridge, Massachusetts 02139-4307, United States.
A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (-), have been formed via molecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (RP-BF-N; -) and involve the release of dinitrogen (N), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (P to P). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds.
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