ABSTRACT
Organophosphorus compounds (OPCs) are highly important chemicals, finding numerous applications in both academia and industry. Herein we describe a simple photocatalytic method for the stannylation of white phosphorus (P4) using a cheap, commercially-available distannane, (Bu3Sn)2, and anthraquinone as a simple photocatalyst. Subsequent 'one pot' transformation of the resulting stannylated monophosphine intermediate (Bu3Sn)3P provides direct, convenient and versatile access to valuable OPCs such as acylated phosphines and tetraalkylphosphonium salts.
ABSTRACT
Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step.
ABSTRACT
The divalent iron complexes trans-[FeBr2(BINC)2], [Cp*FeCl(BINC)] (Cp* = Me5C5), and [FeBr2(CNAr3NC)2] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr3NC (2,2â³-diisocyano-3,5,3â³,5"tetramethyl-1,1':3',1â³-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di- and trinuclear compounds [Fe3(BINC)6], [Cp*Fe(BINC)]2, [Fe(CNAr3NC)2]2, and [K(Et2O)]2[Fe(CNAr3NC)2]2. The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV-vis-NIR spectroelectrochemistry.
