The Al(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr]− and Ar 2,6-Pri2C6H3) reacts with H–X (X H, Si, B, Al, C, N, P, O) σ bonds of H2, silanes, borane (HBpin, pin pinacolate), allane (NacNacAlH2), phosphine (HPPh2), amines, alcohol (PriOH), Cp*H (Cp* pentamethylcyclopentadiene) to give a series hydride derivatives the four-coordinate aluminum NacNacAlH(X), which are characterized herein by spectroscopic methods (NMR IR) X-ray diffraction. This method allows for syntheses first boryl...

Oxidative addition of very robust C–F and C–O bonds has been accomplished in reactions the aluminum(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr]− Ar 2,6-Pri2C6H3) with fluoroarenes, fluoroalkanes, ethers. Similar to transition metals, ease aryl oxidative decreases as degree fluorination diminishes on aromatic substrate. As well, kinetic studies 1,2,3,4-tetrafluorobenzene 1 revealed a second-order reaction characterized by negative entropy activation (ΔS⧧ −113.6(3) J/K·mol),...

Reduction of the cationic Ge(II) complex [dimpyrGeCl][GeCl3] (dimpyr=2,6-(ArN=CMe)2NC5H3, Ar=2,6-iPr2C6H3) with potassium graphite in benzene affords an air sensitive, dark green compound Ge(0), [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This first example zero-valent Group 14 element that does not contain carbene or carbenoid ligand. species has singlet ground state. DFT studies revealed partial delocalization one Ge lone pairs over π*(C=N) orbitals imines. results...

Abstract The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl ( 1 ; NacNac=[ArNC(Me)CHC(Me)NAr] − , Ar=2,6‐Pr i 2 C 6 H 3 ) resulted in oxidative cleavage C=S bond and formation 5 first monomeric aluminum complexes an Al=S double stabilized by N‐heterocyclic carbenes. Compound also reacted triphenylphosphine sulfide a similar manner, which P=S production adduct [NacNacAl=S(S=PPh )] 8 ). can react phenyl isothiocyanate to furnish cycloaddition product 9 zwitterion 10 as...

The cationic aluminum complex [NacNacAlH]+ (2; NacNac = CH{C(Me)N(2,6-Pri2C6H3)}2) can be easily generated from NacNacAlH2 by hydride abstraction and functions as a catalyst for the hydrosilylation of olefins alkynes. Mechanistic studies suggest that, although olefin insertion into Al–H bond is very facile, catalysis does not proceed an insertion/metathesis mechanism but likely Lewis acid activation. Stoichiometric reactions 2 with alkynes furnished unexpected products C≡C addition across...

Abstract Reduction of the cationic Ge II complex [dimpyrGeCl][GeCl 3 ] (dimpyr=2,6‐(ArN=CMe) 2 NC 5 H 3, Ar=2,6‐ i Pr C 6 ) with potassium graphite in benzene affords an air sensitive, dark green compound 0 , [dimpyrGe], which is stabilized by a bis(imino)pyridine platform. This first example zero‐valent Group 14 element that does not contain carbene or carbenoid ligand. species has singlet ground state. DFT studies revealed partial delocalization one lone pairs over π*(CN) orbitals imines....

Preparation of a terminal scandium imido complex, 2·DMAP, was accomplished through thermolysis an arylamido methyl 1, stabilized by bulky β-diketiminato ligand in the presence 4-N,N-dimethylaminopyridine (DMAP). Mechanistic studies revealed that reaction proceeds initial metalation followed rapid DMAP-promoted alkane elimination to generate complex. Kinetic between separately synthesized metalate 3 and DMAP under pseudo-first-order conditions yielded activation parameters ΔH⧧ = 73.5(2) kJ...

Reaction of the cyclic guanidine TolN═SIMe with aluminum(I) compound NacNacAl (1) results in unprecedented cleavage C–N multiple bond to give, after rearrangement, carbene-ligated Al(III) amide, NacNac′Al(NHTol)(SIMe) (6). DFT calculations revealed that these reactions proceed via a bimolecular mechanism which either basic Al(I) center or transient Al═NTol species deprotonates methyl group NacNac ligand.

The aluminum(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis(phenyl sulfide) complex NacNacAl(SPh)2 (2) alkyl thiolate aluminum NacNacAlEt(SEt) (3). As well, reaction of 1 tetraphenyl diphosphine furnishes bis(diphenyl phosphido) NacNacAl(PPh2)2 (4). Production 3 4 are first examples C(sp3)–S R2P–PR2 activation by a main-group element complex. All three complexes were characterized multinuclear NMR spectroscopy X-ray...

The reaction of cyclic urea 1,3-dimethyl-2-imidazolidinone with the aluminum(I) compound NacNacAl (1) gives an unexpected adduct isomerized aluminum(III) hydride NacNac′AlH(O═SIMe) (3). A related 1 phosphine oxides results in cleavage P═O bond and formation hydroxyl derivatives NacNac′Al(OH)(O═PR3) [R = Ph (5) Et (6)]. Density functional theory calculations revealed that these reactions proceed via a bimolecular mechanism which either basic center or transient Al═O species deprotonate methyl...

A rigid NSN-donor proligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylthioxanthene (H2[TXA2], 1) was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylthioxanthene. Deprotonation 1 using nBuLi provided Li2(DME)2[TXA2] (2), and subsequent reaction UCl4 afforded [Li(DME)3][(TXA2)UCl3] (4). The analogous NON-donor ligated complex [(XA2)UCl3K(DME)3] [3; XA2 =...

Abstract The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl ( 1 ; NacNac=[ArNC(Me)CHC(Me)NAr] − , Ar=2,6‐Pr i 2 C 6 H 3 ) resulted in oxidative cleavage C=S bond and formation 5 first monomeric aluminum complexes an Al=S double stabilized by N‐heterocyclic carbenes. Compound also reacted triphenylphosphine sulfide a similar manner, which P=S production adduct [NacNacAl=S(S=PPh )] 8 ). can react phenyl isothiocyanate to furnish cycloaddition product 9 zwitterion 10 as...

Polyanions based on poly(methyl vinyl ether-alt-maleic acid) were investigated as materials for cell encapsulation. These water-soluble polyanions having molecular masses ranging from 20 to 1980 kDa prepared by functionalization of anhydride) with 5-aminofluorescein and/or α-methoxy-ω-amino-poly(ethylene glycol), followed base hydrolysis the residual anhydride groups form corresponding ether-alt-sodium maleate). Their potential replace alginate both in core and, particular, outer shell...

Stepwise reduction of the diiminopyridine complex dimpyrZnCl₂ by KC₈ leads to compounds dimpyrZnCl (<bold>2</bold>), dimpyrZnCl(DMAP) (<bold>3</bold>) and dimpyrZn(DMAP)₂ (<bold>4</bold>) having unusual square-planar see-saw geometries.

Quantification of Cannabinoids Using Benchtop NMR.

Abstract The use of nickel complexes utilizing non‐innocent ligands based on picolinamide to function as redox carriers in flow batteries was explored. moiety linked together with −CH 2 CH − (bpen), (bppn), and −C 6 H 4 (bpb) moieties, resulting two, three, four quasi‐reversible waves, respectively, for the &gt;3 V difference between outermost positive negative waves. events were theoretically modelled each complex, showing excellent agreement (&lt;0.3 difference) experimental potentials....

Redox flow batteries (RFBs) have recently been recognized as a potentially viable technology for scalable energy storage. To take full advantage of RFBs, one possible approach achieving high densities is to maximize number redox events by utilizing charge carriers capable multiple one-electron transfers within the electrochemical window solvent. However, past efforts develop more efficient electrolytes nonaqueous RFBs mostly empirical. In this manuscript, we shed light on design principles...