Quest for Active Species in Al/B-Catalyzed CO2 Hydrosilylation.

We demonstrate the catalytic role of aluminum and boron centers in aluminum borohydride [(2-Me2CH2C6H4)(C6H5)Al(µ-H)2B(C6H5)2] (6) during carbon dioxide (CO2) hydrosilylation. Preliminary investigations into CO2 reduction using [(2-Me2NCH2C6H4)(H)Al(µ-H)]2 (1) and [Ph3C][B(3,5-C6H3Cl2)4] (2) in the presence of Et3SiH and PhSiH3 resulted in CH2(OSiR3)2 and CH3OSiR3, which serve as formaldehyde and methanol surrogates, respectively. In pursuit of identifying the active catalytic species, three compounds, B(3,5-C6H3Cl2)3 (3), [(2-Me2NCH2C6H4)(3,5-C6H3Cl2)Al(µ-H)2B(3,5-C6H3Cl2)2] (4), and [(2-Me2NCH2C6H4)2Al(THF)][B(3,5-C6H3Cl2)4] (5), were isolated. Among compounds 2-5, the highest catalytic conversion was achieved by 4. Further, 4 and 6 were prepared in a straightforward method by treating 1 with 3 and BPh3, respectively. 6 was found to be in equilibrium with 1 and BPh3, thus making the catalytic process of 6 more efficient than that of 4. Computational investigations inferred that CO2 reduction occurs across the Al-H bond, while Si-H activation occurs through a concerted mechanism involving an in situ generated aluminum formate species and BPh3.

From Sn(II) to Sn(IV): Enhancing Lewis Acidity Via Oxidation.

We demonstrate the increased Lewis acidity on going from Sn(II) to Sn(IV) by oxidizing TpMe2SnOTf (OTf = SO3CF3) to TpMe2SnF(OTf)2. Replacement of the fluoride ion in TpMe2SnF(OTf)2 by a triflate, resulting in TpMe2Sn(OTf)3 further enhances the Lewis acidity at tin. 119Sn NMR spectroscopy, modified Gutmann-Beckett test, computational analysis, and catalytic phosphine oxide deoxygenation support the claims.

Reactivity of a quasi-four-coordinate butylmagnesium cation.

We present the reactivity of the Mg-C and the ß-CH bonds in the trigonal pyramidal [(pmdta)Mg(nBu)]+ exhibiting a weak Mg⋯F interaction with counter anion, [B(C6F5)4]-. Instantaneous ß-hydride reactivity with benzophenone, reductive alkylation of phenyl benzoate, and straightforward synthesis of [(pmdta)MgH]+via metathesis with pinacolborane/phenylsilane are discussed.

Crystallographic evidence for a continuum and reversal of roles in primary-secondary interactions in antimony Lewis acids: applications in carbonyl activation.

Primary and secondary interactions form the basis of substrate activation in Lewis-acid mediated catalysis, with most substrate activations occurring at the secondary binding site. We explore two series of antimony cations, [(NMe2CH2C6H4)(mesityl)Sb]+ (A) and [(NMe2C6H4)(mesityl)Sb]+ (B), by coordinating ligands with varying nucleophilicity at the position trans to the N-donor. The decreased nucleophilicity of the incoming ligands leads to reversal from a primary bond to a secondary interaction in A, whereas a constrained N-coordination in B diminishes the border between primary and secondary bonding. Investigations on carbonyl olefin metathesis reactions and carbonyl reduction demonstrate increased reactivity of a Lewis acid when the substrate activation occurs at the primary binding site.

Novel biologically synthesized metal nanopowder from wastewater for dye removal application.

A novel adsorbent based on metal sulfide nanoparticles (MeSNPs) was biologically synthesized from metallic wastewater and examined for azo dyes removal from aqueous solution in batch and continuous systems. The size of the MeSNPs was in the range of 8-10 nm, with an average specific surface area of 120.4 m2/g. Batch adsorption study was then carried out using Direct Red 80 (DR 80) and Mordant Blue 9 (MB 9) as the model azo dyes by varying MeSNPs dosage, contact time, pH, and initial dye concentration. More than 99% removal efficiency of both the dyes was achieved by using MeSNPs at the following optimum conditions: 200 mg dosage, pH 2, 6 min contact time, and 100 mg L-1 initial dye concentration. The batch sorption isotherm results were described using the Sips model, with the maximum predicted capacity values of 143.7 and 198.3 mg of dye per gram of adsorbent for DR 80 and MB 9, respectively. Besides, the sorption kinetic data for both the dyes followed the pseudo-second-order rate. Furthermore, maximum desorption efficiency values of 93% for DR 80 and 97% for MB 9 were achieved using an aqueous solution of pH 12, thus indicating that the adsorbent can be regenerated and reused further. Dynamic adsorption of the dyes was studied using a fixed-bed column with the MeSNPs as a function of liquid flow rates. The results showed an increase in breakthrough time with a decline in the flow rates for both DR 80 and MB 9 and the breakthrough behavior was explained using Thomas, Clark, and Yoon-Nelson models.

Reversing Lewis acidity from bismuth to antimony.

Investigations on the boundaries between the neutral and cationic models of (Mesityl)2EX (E = Sb, Bi and X = Cl-, OTf-) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl)2SbOTf over (Mesityl)2BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.

Cationic Zinc Hydride Catalyzed Carbon Dioxide Reduction to Formate: Deciphering Elementary Reactions, Isolation of Intermediates, and Computational Investigations.

Zinc has been an element of choice for carbon dioxide reduction in recent years. Zinc compounds have been showcased as catalysts for carbon dioxide hydrosilylation and hydroboration. The extent of carbon dioxide reduction can depend on various factors, including electrophilicity at the zinc center and the denticity of the ancillary ligands. In a few cases, the addition of Lewis acids to zinc hydride catalysts markedly influences carbon dioxide reduction. These factors have been investigated by exploring elementary reactions of carbon dioxide hydrosilylation and hydroboration by using cationic zinc hydrides bearing tetradentate tris[2-(dimethylamino)ethyl]amine and tridentate N,N,N',N'',N''-pentamethyldiethylenetriamine in the presence of triphenylborane and tris(pentafluorophenyl)borane.

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation.

Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2 NC6 H4 )Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2 NC6 H4 }Bi{OP(NMe2 )3 }3 ][B(3,5-C6 H3 Cl2 )4 ]2 . These observations led us to generate dicationic organobismuth catalyst, [(Me2 NC6 H4 )Bi(L)3 ]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si-H addition.

Organoaluminum cations for carbonyl activation.

In search of stable, yet reactive aluminum Lewis acids, we have isolated an organoaluminum cation, [(Me2NC6H4)2Al(C4H8O)2]+, coordinated with two labile tetrahydrofuran ligands. Its catalytic performance in aldehyde dimerization reveals turn-over frequencies reaching up to 6000 h-1, exceeding that of the reported main group catalysts. The cation is further demonstrated to catalyze hydroelementation of ketones. Mechanistic investigations reveal that aldehyde dimerization and ketone hydrosilylation occur through carbonyl activation.

Amidomagnesium cations.

We report the synthesis, structure and reactivity of molecular amidomagnesium cations bearing tris{2-(dimethylamino)-ethyl}amine (Me6TREN). Me6TREN binds to the cationic magnesium centre exhibiting κ4 and κ3 coordination modes in [Me6TREN-Mg-N(SiHMe2)2]+ and [Me6TREN-Mg-N(SiMe3)2]+ respectively. [Me6TREN-Mg-N(SiHMe2)2]+ reacts with benzophenone resulting in the insertion of the carbonyl group across ß-SiH bond. The reaction between [Me6TREN-Mg-N(SiMe3)2]+ and CO2 leads to [Me6TREN-Mg-OSiMe3]+, while the reaction with H2O results in [Me6TREN-Mg-OH]22+. Attempts to prepare hydridomagnesium cations from [Me6TREN-Mg-N(SiMe3)2]+ using KH resulted in the precipitation of MgH2 and the isolation of [(Me6TREN)K(THF)3]+.

Terminal hydridozinc cation.

A thermally stable terminal hydridozinc cation has been isolated. The nucleophilicity of the hydride ligand is demonstrated by inserting carbon dioxide, carbodiimide and benzophenone across the Zn-H bond in a facile manner. Preliminary studies on catalytic hydrosilylation using PhSiH3 indicate that the hydridozinc cation in the presence of BPh3 can selectively reduce CO2 to PhSi(OCHO)3.

A disguised hydride in a butylmagnesium cation.

The ability of the ß-CH functionality in a butylmagnesium cation [Me6TREN-Mg-n-Bu]+ to quantitatively reduce benzophenone has been demonstrated. The hydridic nature of the ß-CH functionality is highlighted by its abstraction using B(C6F5)3. ß-CH abstraction over alkylation in [Me6TREN-Mg-n-Bu]+ is dependent on the nature of the incoming electrophile and the polarity of the solvent.

Consequence of Ligand Bite Angle on Bismuth Lewis Acidity.

Ligand bite angle, a common parameter to fine-tune reactivity in transition-metal chemistry, is used for the first time in main-group chemistry to control and tune the Lewis acidity in organobismuth cations bearing 2-[(dimethylamino)methyl]phenyl (Me2NCH2C6H4) and 2-(dimethylamino)phenyl (Me2NC6H4) ligands. The latter chelating ligand induces a shorter C-Bi-N bite angle, leading to a weaker Bi-N bond with a corresponding lower Bi-N σ*-acceptor orbital and hence exhibiting remarkably higher Lewis acidity. The Gutmann-Beckett method is successfully employed to quantify the Lewis acidity in organobismuth cations.

Manifestation of helicity in one-dimensional iodobismuthate.

We report here, the first example of an inorganic-organic hybrid material incorporating a helical iodobismuthate [BiI4]∞ templated by 2,6-diisopropylanilinium cations. The realisation of the helical iodobismuthate opens up the possibility of a wide range of physical properties among hybrid materials.

Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

A hydride-ligated dysprosium single-molecule magnet.

An experimental and ab initio computational study of an unsymmetrical, hydride-bridged di-dysprosium single-molecule magnet is reported.

Dihydrogen addition in a dinuclear rare-earth metal hydride complex supported by a metalated TREN ligand.

The dinuclear lutetium dihydride dication supported by metalated tripodal ligands undergoes facile hydrogenolysis with H(2) to form a trihydride dication. Molecular orbital analysis shows that the LUMO is a bonding Lu···Lu orbital that is poised to activate dihydrogen.

C-H activation versus yttrium-methyl cation formation from [Y(AlMe4)3] induced by cyclic polynitrogen bases: solvent and substituent-size effects.

The reaction of 1,3,5-triisopropyl-1,3,5-triazacyclohexane (TiPTAC) with [Y(AlMe(4))(3)] resulted in the formation of [(TiPTAC)Y(Me(3)AlCH(2)AlMe(3))(µ-MeAlMe(3))] by C-H activation and methane extrusion. In contrast, the presence of bulkier cyclohexyl groups on the nitrogen atoms in 1,3,5-tricyclohexyl-1,3,5-triazacyclohexane (TCyTAC) led to the formation of the cationic dimethyl complex [(TCyTAC)(2)YMe(2)][AlMe(4)]. The investigations reveal a dependency of the reaction mechanism on the steric bulk of the N-alkyl entity and the solvent employed. In toluene C-H activation was observed in reactions of [Y(AlMe(4))(3)] with 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) and TiPTAC. In THF molecular dimethyl cations, such as [(TCyTAC)(2)YMe(2)][AlMe(4)], [(TMTAC)(2)YMe(2)][AlMe(4)] and [(TiPTAC)(2)YMe(2)][AlMe(4)], could be synthesised by addition of the triazacyclohexane at a later stage. The THF-solvated complex [YMe(2)(thf)(5)][AlMe(4)] could be isolated and represents an intermediate in these reactions. It shows that cationic methyl complexes of the rare-earth metals can be formed by donor-induced cleavage of the rare-earth-metal tetramethylaluminates. The compounds were characterised by single-crystal X-ray diffraction or multinuclear and variable-temperature NMR spectroscopy, as well as elemental analyses. Variable-temperature NMR spectroscopy illustrates the methyl group exchange processes between the cations and anions in solution.

Ping-pong at gold: proton jump between coordinated phenyl and eta1-benzene ligands, a computational study.

A DFT computational investigation predicts that the Au(III) complex (bpy)Au(C(6)H(5))(2+) reacts with benzene to furnish square planar (bpy)Au(C(6)H(5))(eta(1)-C(6)H(6))(2+). Intramolecular processes that occur within this species have been located, and the energetics of all processes have been quantified. The dynamic processes that have been identified are (1) benzene ring rotation with respect to Au, (2) direct hydrogen transfer from the benzene to the phenyl ligand, (3) hydrogen transfer from the ipso to the ortho positions in the coordinated benzene ligand, and (4) hydrogen transfer from the benzenium ligand formed by the ipso/ortho isomerization to the phenyl ligand. Similarities and differences are seen between the behavior of (bpy)Au(C(6)H(5))(eta(1)-C(6)H(6))(2+) and previously reported isoelectronic Pt(II) complexes. Preliminary experimental results related to this chemistry are reported, and possible consequences for C-H bond activation mediated by gold are discussed.