NH bond activation of ammonia and amines by ditetrelenes: key insights into the stereochemistry of nucleophilic addition.

The NH bond activation of ammonia, primary and secondary amines by tetramesityldisilene and -digermene was investigated. In each case, a disilyl- or digermylamine was formed as the only product of amine addition. The mechanism of the addition of ammonia to tetramesityldisilene was computed and revealed a three-step reaction pathway: formation of the anti-ammonia-disilene adduct, inversion at the ß-silicon, and syn-transfer of the proton to give the syn-product, where each step follows a distinct stereochemical course. Examination of the reaction landscape also revealed several additional insights: (a) that, in the initial step, the formation of the anti-oriented zwitterionic intermediate is kinetically more preferable than formation of the syn-oriented zwitterionic intermediate, (b) that intermolecular transfer of a proton is not energetically feasible in non-polar solvents, and (c) that the bulk of the substituents can have a profound effect on the stereochemical course of the reaction. With this detailed understanding, nucleophilic additions to ditetrelenes can be exploited in the future.

Synthesis and Reactivity of Cationic Gallium(I) [12]Crown-4 Complexes.

The synthesis and reactivity of a gallium(I) cationic complex using [12]crown-4 as a stabilizing ligand were explored. The synthesis of [Ga([12]crown-4)][GaCl4] was achieved in one step from commercially available starting materials. Anion exchange was utilized to replace the reactive tetrachlorogallate anion for the perfluorophenylborate anion. [Ga([12]crown-4)][B(C6F5)4] was analyzed using XPS, which allowed for the classification of the gallium(I)-crown ether complex as electron-deficient. Reactions of the gallium(I)-crown ether complex with Cp*K and cryptand[2.2.2] demonstrated the facile synthesis of a known gallium(I) compound as well as the generation of new gallium(I) complexes, highlighting the use of the gallium(I)-crown ether complex as an effective starting material for new gallium(I) complexes.

Chlorine-35 Solid-State Nuclear Magnetic Resonance Spectroscopy as an Indirect Probe of the Oxidation Number of Tin in Tin Chlorides.

Ultrawideline 35Cl solid-state nuclear magnetic resonance (SSNMR) spectra of a series of 12 tin chlorides were recorded. The magnitude of the 35Cl quadrupolar coupling constant (CQ) was shown to consistently indicate the chemical state (oxidation number) of the bound Sn center. The chemical state of the Sn center was independently verified by tin Mössbauer spectroscopy. CQ(35Cl) values of >30 MHz correspond to Sn(IV), while CQ(35Cl) readings of <30 MHz indicate that Sn(II) is present. Tin-119 SSNMR experiments would seem to be the most direct and effective route to interrogating tin in these systems, yet we show that ambiguous results can emerge from this method, which may lead to an incorrect interpretation of the Sn oxidation number. The accumulated 35Cl NMR data are used as a guide to assign the Sn oxidation number in the mixed-valent metal complex Ph3PPdImSnCl2. The synthesis and crystal structure of the related Ph3PPtImSnCl2 are reported, and 195Pt and 35Cl SSNMR experiments were also used to investigate its Pt-Sn bonding. Plane-wave DFT calculations of 35Cl, 119Sn, and 195Pt NMR parameters are used to model and interpret experimental data, supported by computed 119Sn and 195Pt chemical shift tensor orientations. Given the ubiquity of directly bound Cl centers in organometallic and inorganic systems, there is tremendous potential for widespread usage of 35Cl SSNMR parameters to provide a reliable indication of the chemical state in metal chlorides.

The Diverse Reactivity of Disilenes Toward Isocyanides.

The addition of 2,6-dimethylphenyl isocyanide and t-butyl isocyanide to tetramesityldisilene was examined. In both cases, the initially formed product is an iminodisilirane; however, the iminodisiliranes are unstable under the reaction conditions and react with a second equivalent of the isocyanide to give either a 3-silaazetidine or a novel bicyclic double enamine, respectively. Taken together with the previous examples in the literature, the results demonstrate that subtle differences in the steric bulk of the disilene or the electronic effects of the isocyanide can lead to dramatic differences in the reaction pathway.

Reactivity of sulfonyl-containing compounds with ditetrelenes.

The addition of a variety of sulfones and a sulfoxide to ditetrelenes (a disilene and a digermene) was examined. The reaction of benzenesulfonyl chloride with tetramesityldisilene or tetramesityldigermene results in the formation of the 1,2-addition products, 2-chlorotetramesityldisilyl- or digermylbenzenesulfinate. The addition of p-toluenesulfonyl chloride to the disilene gave the analogous product, 2-chlorotetramesityldisilyl p-toluenesulfinate. In contrast, benzenesulfonyl fluoride, diphenyl and dimethyl sulfone did not react with either the disilene or the digermene. The unprecedented formation of the sulfinates reveals a selective 2-electron reduction of the sulfur centres using ditetrelenes. The addition reactions of sulfonyl compounds illustrates the potential of ditetrelenes to serve as reducing agents which react rapidly, at room temperature under mild conditions. The reaction of tetramesityldisilene with diphenyl sulfoxide resulted in the formation of tetramesityloxadisilirane and with benzene sulfonic acid resulted in the formation of 1,1,2,2-tetramesityldisilyl benzenesulfonate.

Beyond Oxidation States: Distinguishing Chemical States of Gallium in Compounds with Multiple Gallium Centers.

The electronic structures of a series of gallium complexes are examined using X-ray absorption spectroscopy (XAS) in combination with ab initio calculations. The chemical states of Ga are strongly affected by the ligands and the bonding environment. For complexes containing multiple gallium sites, we demonstrate that XAS can identify the chemical state of each unique gallium center. A reliable understanding of the chemical nature of the core element in a coordination complex with strong core-ligand interaction can be obtained only when both experimental and theoretical approaches are combined.

Addition of Isocyanides to Tetramesityldigermene: A Comparison of the Reactivity between Surface and Molecular Digermenes.

The reaction of benzyl isocyanide, tert-butyl isocyanide, and 2,6-dimethylphenyl isocyanide with tetramesityldigermene (Mes2 Ge=GeMes2 ) was examined. Whereas the addition of benzyl isocyanide gave the C-NC activation product, Mes2 Ge(CH2 Ph)Ge(CN)Mes2 , tert-butyl isocyanide, and 2,6-dimethylphenyl isocyanide did not give stable adducts, rather the rate of conversion of the digermene to the corresponding cyclotrigermane was accelerated. A comparison between the reactivity of the isocyanides with Mes2 Ge=GeMes2 and the Ge(100)-2×1 surface was made and some insights into the surface chemistry are offered.

Chemical state determination of molecular gallium compounds using XPS.

A series of molecular gallium compounds were analyzed using X-ray photoelectron spectroscopy (XPS). Specifically, the Ga 2p3/2 and Ga 3d5/2 photoelectron binding energies and the Ga L3M45M45 Auger electron kinetic energies of compounds with gallium in a range of assigned oxidation numbers and with different stabilizing ligands were measured. Auger parameters were calculated and used to generate multiple chemical speciation (or Wagner) plots that were subsequently used to characterize the novel gallium-cryptand[2.2.2] complexes that possess ambiguous oxidation numbers for gallium. The results presented demonstrate the ability of widely accessible XPS instruments to experimentally determine the chemical state of gallium centers and, as a consequence, provide deeper insights into reactivity compared to assigned oxidation and valence numbers.

Synthesis and Characterization of Cationic Low-Valent Gallium Complexes of Cryptand[2.2.2].

The synthesis and characterization of two bimetallic, cationic low-valent gallium-cryptand[2.2.2] complexes is reported. The reaction of cryptand[2.2.2] with Ga2Cl4 gave two different cations, [Ga3Cl4 (crypt-222)](+) (1) or [Ga2Cl2 (crypt-222)](2+) (2), depending on whether or not trimethylsilyl triflate (Me3SiOTf) was added as a co-reagent. Complexes 1 and 2 are the first examples of bimetallic cryptand[2.2.2] complexes, as well as the first low-valent gallium-cryptand[2.2.2] complexes. Computational methods were used to evaluate the bonding in the gallium cores.