Ammonium and Potassium Salts of a Hexacoordinate Phosphorus(V) Anion Featuring P-O and P-C Bonds.

Ammonium and potassium salts featuring the chiral mer-[P(CHCO)], mer-[1], have been isolated. Specifically, treating phosphorane P(CHCO)(CHCOH), 2, with N-containing bases [N = PhNMe, PhNH, pyridine (py), isoquinoline, (-)-brucine, N( n-CH)] afforded ammonium salts [NH]- mer-[1]. Each compound was fully characterized spectroscopically, and four were subjected to X-ray crystallographic analysis.

[HL][P(1,2-OCCl)] (L = THF, DMF): Brønsted acid initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene.

The development of solid, weighable Brønsted acids featuring the hexacoordinated phosphorous(v) anion [TRISPHAT] are reported. H(DMF)[1] and H(THF)[1] {[1] = [P(1,2-OCCl)]} were synthesized and fully characterized by H, P, C and 2D-NOESY NMR spectroscopy, X-ray crystallography, mass spectrometry and elemental analysis. Both, H(DMF)[1] and H(THF)[1] are found to be suitable initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene.

Strong Evidence of a Phosphanoxyl Complex: Formation, Bonding, and Reactivity of Ligated Phosphorus Analogues of Nitroxides.

Facile access to [W(CO) (Ph P-OTEMP)] is used to initiate a study on the generation, properties, and reactions of transient phosphanoxyl complexes [ML (R PO)], the first example of which could be trapped via heterocoupling with the trityl radical. It is also demonstrated that the phosphorus nitroxyl complex acts as radical initiator in the polymerization of styrene. The quest for P-O versus O-N bond homolysis, as well as the initial steps of the polymerization were studied by DFT methods.

Electronic Structure Description of a Doubly Oxidized Bimetallic Cobalt Complex with Proradical Ligands.

The geometric and electronic structure of a doubly oxidized bimetallic Co complex containing two redox-active salen moieties connected via a 1,2-phenylene linker was investigated and compared to an oxidized monomeric analogue. Both complexes, namely, CoL(1) and Co2L(2), are oxidized to the mono- and dications, respectively, with AgSbF6 and characterized by X-ray crystallography for the monomer and by vis-NIR (NIR = near-infrared) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and density functional theory (DFT) calculations for both the monomer and dimer. Both complexes exhibit a water molecule coordinated in the apical position upon oxidation.

Class III delocalization and exciton coupling in a bimetallic bis-ligand radical complex.

The geometric and electronic structure of an oxidized bimetallic Ni complex incorporating two redox-active Schiff-base ligands connected via a 1,2-phenylene linker has been investigated and compared to a monomeric analogue. Information from UV/Vis/NIR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, electrochemistry, and density functional theory (DFT) calculations provides important information on the locus of oxidation for the bimetallic complex. The neutral bimetallic complex is conformationally dynamic at room temperature, which complicates characterization of the oxidized forms.

H(OEt2)2[P(1,2-O2C6Cl4)3]: synthesis, characterization, and application as a single-component initiator for the carbocationic polymerization of olefins.

The development of novel Brønsted acids featuring the hexacoordinate phosphorus(V) anion [TRISPHAT](-) {[1](-)=[P(1,2-O2C6Cl4)3](-)} are reported. The title compound, H(OEt2)2[1], was synthesized from 1,2-(HO)2C6Cl4 (3 equiv) and PCl5 in the presence of diethyl ether. This compound was fully characterized by (1)H, (31)P and (13)C NMR spectroscopy, X-ray crystallography and elemental microanalysis.

Double oxidation localizes spin in a Ni bis-phenoxyl radical complex.

The electronic structure of a doubly oxidized Ni salen complex NiSal(tBu) (Sal(tBu) = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) has been investigated by both experimental and theoretical methods. The doubly oxidized product was probed by resonance Raman spectroscopy, UV-vis-NIR, and EPR to determine the locus of oxidation as well as the spectroscopic signature of the complex. It was determined that double oxidation of NiSal(tBu) affords a bis-ligand radical species in solution via the presence of phenoxyl radical bands at ν(7a) (1504 cm(-1)) and ν(8a) (1579 cm(-1)) in the Raman spectrum, and the loss of the intense NIR transition reported for the mono-radical complex (Angew.