Fluorination/Dearomatization of CF Groups: An FLP Route to an Electrophilic Borane and Non-Coordinating Anions.

B(CF) and the corresponding anion [B(CF)] are ubiquitous in main group and transition metal chemistry. Known derivatives are generally limited to the incorporation of electron donating substituents. Herein we describe electrophilic fluorination and dearomatization of such species using XeF in the presence of BF or Lewis acidic cations.

Addition and NN bond cleavage of diazo-compounds by phosphino-phosphenium cations.

The phosphino-phosphenium cation (PPC) [PhPPPh][GaCl] reacts as a frustrated Lewis pair to add across the NN bond of (BuOCN). In contrast, photolytical addition [PhClPPPh][GaCl] to (RN) results in cleavage of the NN bond affording [PhP(μ-NR)PPhCl][GaCl] (R = Ph 2, CHCl). While the chloride of 2 is replaced with N or CN reaction with MeSiN or BuNC respectively, reaction with (CF)BH effects ring opening to give [HN(Ph)PPh(μ-NPh)PPh][GaCl] 7.

Phosphino-Phosphination Reactions: Frustrated Lewis Pair Reactivity of Phosphino-Phosphonium Cations with Alkynes.

The phosphino-phosphonium cations of the form [R PPR' ] are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair-type addition reactions to alkynes, affording unprecedented phosphino-phosphination reactions and giving cations of the form [cis-R PCHC(R'')PR' ] . This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis-olefin-linked bidentate phosphines.

Reactive FLP-alkyne addition products: a route to anionic and zwitterionic phosphines.

Combination of a phosphinidene precursor, B(CF) and 4-ethynyltoluene afforded the FLP addition product, EtN(CH)PC(Tol)CH (B(CF)) 2. Compound 2 reacted with halides, pseudo-halides or MeSiSPh to provide a facile route to the salts of anionic phosphines while reaction with PEt gave the zwitterion EtPCHC(SiMe)P(NEt)C(Tol)CHB(CF)8. This latter species reacted with an alkyne to give a phosphine donor with both olefin-linked cationic and anionic substituents.

Synthesis of α,δ-Disubstituted Tetraphosphates and Terminally-Functionalized Nucleoside Pentaphosphates.

The anion [PO], employed as its bis(triphenylphosphine)iminium (PPN) salt, is shown herein to be a versatile reagent for nucleophile tetraphosphorylation. Treatment under anhydrous conditions with an alkylamine base and a nucleophile (HNuc), such as an alcohol (neopentanol, cyclohexanol, 4-methylumbelliferone, and Boc-Tyr-OMe), an amine (propargylamine, diethylamine, morpholine, 3,5-dimethylaniline, and isopropylamine), dihydrogen phosphate, phenylphosphonate, azide ion, or methylidene triphenylphosphorane, results in nucleophile substituted tetrametaphosphates ([PONuc]) as mixed PPN and alkylammonium salts in 59% to 99% yield. Treatment of the resulting functionalized tetrametaphosphates with a second nucleophile (HNuc), such as hydroxide, a phenol (4-methylumbelliferone), an amine (propargylamine and ethanolamine), fluoride, or a nucleoside monophosphate (uridine monophosphate, deoxyadenosine monophosphate, and adenosine monophosphate), results in ring opening to linear tetraphosphates bearing one nucleophile on each end ([Nuc(PO)PONuc]).

An arene-stabilized η-pentamethylcyclopentadienyl antimony dication acts as a source of Sb or Sb cations.

Double chloride abstraction from Cp*SbCl2 (Cp* = pentamethylcyclopentadienyl) affords an arene-stabilized η5-Cp*-bound antimony dicationic compound [(η5-Cp*)Sb(tol)][B(C6F5)4]2 (1) (tol = toluene), which exhibits strong Lewis acidity, abstracting chloride from Ph3CCl. 1 reacts with different Lewis bases via divergent pathways, giving rise to release of either Sb+ or Sb3+ cations.

Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalate Esters.

A nickel-catalyzed cyanation reaction of benzylic and allylic pivalate esters is reported using an air-stable Ni(II) precatalyst and substoichiometric quantities of Zn(CN). Alkene additives were found to inhibit catalysis, suggesting that avoiding β-hydride elimination side reactions is essential for productive catalysis. An enantioenriched allylic ester undergoes enantiospecific cross-coupling to produce an enantioenriched allylic nitrile.

Controlling charge transport mechanisms in molecular junctions: Distilling thermally induced hopping from coherent-resonant conduction.

The electrical conductance of molecular junctions may depend strongly on the temperature and weakly on molecular length, under two distinct mechanisms: phase-coherent resonant conduction, with charges proceeding via delocalized molecular orbitals, and incoherent thermally assisted multi-step hopping. While in the case of coherent conduction, the temperature dependence arises from the broadening of the Fermi distribution in the metal electrodes, in the latter case it corresponds to electron-vibration interaction effects on the junction. With the objective to distill the thermally activated hopping component, thus exposing intrinsic electron-vibration interaction phenomena on the junction, we suggest the design of molecular junctions with "spacers," extended anchoring groups that act to filter out phase-coherent resonant electrons.