Contrasting reactivity of B-Cl and B-H bonds at [Ni(IMes)2] to form unsupported Ni-boryls.

[Ni(IMes)2] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B-Cl activation proceeds via nucleophilic displacement of Cl-, while B-H activation would entail high energy concerted bond cleavage.

Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions.

We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events-the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions.

Synthesis and Reactivity of Triangular Heterometallic Complexes Containing Zn-Zn Bond.

This work provides a facile access to a series of triangular [Zn2M] (M = group 10 and 11 metals) clusters. Treatment of Zn-Zn-bonded compounds [LZn-ZnL] (L = CH3C(2,6-iPr2C6H3N)CHC(CH3)(NCH2CH2PR2); R = Ph, iPr) with zero-valent transition-metal reagents selectively afforded the corresponding triangular clusters [Zn2M], where M = Ni(0), Pd(0), and Pt(0). Notably, the isoelectronic triangular clusters [Zn2M]+, where M = Ag(I) and Cu(I), could also be obtained by reactions of [LZn-ZnL] with AgOTf and CuOTf, respectively. The [Zn2Ag]+ complex containing elusive Zn-Ag bonds was investigated by density functional theory analysis, showing a 3c-2e bonding feature in the metallic ring. The electrochemical behaviors of [Zn2M] complexes were examined and revealed the donation of electron density from the Zn-Zn σ-bond to the metal centers. Reaction of the [Zn2Ni] complex with isocyanide gave heterometallic species by coordination of isocyanide to the nickel center, keeping the trimetallic ring core structure intact. In contrast, the Zn-Zn bond was rapidly cleaved upon treatment of the [Zn2Ni] complex with dihydrogen or phenyl acetylene, generating the hydride- or acetylide-bridged heterotrimetallic complex.

Activation of CO Using a 1,2-Disilylene: Facile Synthesis of an Abnormal N-Heterocyclic Silylene.

Reaction of the 1,2-disilylene, [{ArC(NDip)2 }Si]2 1 (Dip=2,6-diisopropylphenyl, Ar=4-C6 H4 But ), with CO proceeds via insertion of CO into one Si-N bond, and Si-Si bond cleavage, to cleanly give the bis(silylene), {ArC(NDip)2 }Si(:)O C S i ( : ) ( N D i p )​ 2 C ‾ Ar 2, under ambient conditions. The reaction can be partially reversed when solutions of 2 are subjected to UV irradiation. The five-membered heterocyclic fragment of 2 represents the first silicon analogue of an "abnormal" N-heterocyclic carbene (aNHC), a view which is substantiated by a computational analysis of the compound. Reaction of 2 with [Mo(CO)6 ] under UV light affords the chelate complex, [Mo(CO)4 (κ2 -Si,Si-2)] 3, while reaction with [Fe(CO)5 ] gives the unusual silyleneyl bridged complex, [{Fe2 (CO)6 }{µ-Si[(NDip)2 CAr]}2 ] 4. The same coordination complexes can be accessed by reaction of 1 with [Mo(CO)6 ] or [Fe(CO)5 ] under UV light. As is the case for aNHCs, d-block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.

Strontium Hydride Cations Supported by a Large NNNNN Type Macrocycle: Synthesis, Structure, and Hydrofunctionalization Catalysis.

The use of the 15-membered NNNNN macrocyclic ligand Me5PACP (Me5PACP = 1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) allowed the isolation of two cationic strontium hydride complexes by hydrogenolysis of benzyl precursors. Treatment of sparingly soluble [(Me5PACP)Sr(CH2Ph)2] with dihydrogen gave free Me5PACP, toluene, and oligomeric strontium hydride [SrH2]n, while hydrogenolysis in the presence of 1 equiv of the benzyl cation [(Me5PACP)Sr(CH2Ph)][B(C6H3-3,5-Me2)4] enabled isolation of the thermally unstable trihydride cation [(Me5PACP)2Sr2(µ-H)3][B(C6H3-3,5-Me2)4]. When the benzyl cation [(Me5PACP)Sr(CH2Ph)][BAr4]2 (Ar = C6H3-3,5-Me2 or C6H4-4-nBu) was reacted with dihydrogen or n-octylsilane, dihydride complexes [(Me5PACP)2Sr2(µ-H)2][BAr4]2 containing a dinuclear core bridged by two hydride ligands were obtained. The soluble dihydride complex [(Me5PACP)2Sr2(µ-H)2][B(C6H4-4-nBu)4]2 was tested in olefin hydrogenation and hydrosilylation catalysis. Kinetic analyses for [(Me5PACP)2Sr2(µ-H)2]2+ showed lower catalytic activity as compared to that of the isostructural calcium homologue [(Me5PACP)2Ca2(µ-H)2]2+. This is explained by a shift in the monomer-dimer equilibrium which precedes the catalytic cycle.

Exploring the Redox Properties of Bench-Stable Uranyl(VI) Diamido-Dipyrrin Complexes.

The uranyl complexes UO2(OAc)(L) and UO2Cl(L) of the redox-active, acyclic diamido-dipyrrin anion L- are reported and their redox properties explored. Because of the inert nature of the complexes toward hydrolysis and oxidation, synthesis of both the ligands and complexes was conducted under ambient conditions. Voltammetric, electron paramagnetic resonance spectroscopy, and density functional theory studies show that one-electron chemical reduction by the reagent CoCp2 leads to the formation of a dipyrrin radical for both complexes [Cp2Co][UO2(OAc)(L•)] and [Cp2Co][UO2Cl(L•)].

Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation.

The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (thf)4 (µ-κ3 : κ3 -SiH6 )][A]2 (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)Sr(SiH3 )(thf)2 ][A], with release of H2 . Upon reaction with a weak Brønsted acid, CO2 , and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH5 n Oct)][A].

A Brønsted Acidic Gallium Hydride: Facile Interconversion of NNNN-Macrocycle Supported [GaI ]+ and [GaIII H]2.

Protonolysis of [Cp*M] (M=Ga, In, Tl) with [(Me4 TACD)H][BAr4 Me ] (Me4 TACD=N,N',N'',N'''-tetramethyl-1,4,7,10-tetraazacyclododecane; [BAr4 Me ]- =[B{C6 H3 -3,5-(CH3 )2 }4 ]- ) provided monovalent salts [(Me4 TACD)M][BAr4 Me ], whereas [Cp*Al]4 yielded trivalent [(Me4 TACD)AlH][BAr4 Me ]2 . Protonation of [(Me4 TACD)Ga][BAr4 Me ] with [Et3 NH][BAr4 Me ] gave an unusually acidic (pKa (CH3 CN)=24.5) gallium(III) hydride dication [(Me4 TACD)GaH][BAr4 Me ]2 . Deprotonation with IMe4 (1,3,4,5-tetramethyl-imidazol-ylidene) returned [(Me4 TACD)Ga][BAr4 Me ]. These reversible processes occur with formal two-electron oxidation and reduction of gallium. DFT calculations suggest that gallium(I) protonation is facilitated by strong coordination of the tetradentate ligand, which raises the HOMO energy. High nuclear charge of [(Me4 TACD)GaH]2+ facilitates hydride-to-metal charge transfer during deprotonation. Attempts to prepare a gallium(III) dihydride cation resulted in spontaneous dehydrogenation to [(Me4 TACD)Ga]+ .

Nickel-catalyzed synthesis of Zn(I)-Zn(I) bonded compounds.

This work reports the first catalyzed synthesis of d-block metal-metal bonded complexes. The treatment of terminal zinc hydrides [LZnH] [L = CH3C(2,6-iPr2C6H3N)CHC(CH3)(N(CH2)nCH2PR2); n = 1, 2; R = Ph, iPr] in the presence of 5 mol% Ni(CO)2(PPh3)2 afforded Zn(I)-Zn(I) bonded compounds [L2Zn2] in high isolated yields with concomitant elimination of dihydrogen. Stoichiometric reactions, kinetic studies and DFT calculations were conducted to elucidate the reaction mechanism.

Redox-induced reversible P-P coupling in a uranium complex.

A synthesized redox-active multidentate N-P ligand reacted with UCl4 in the presence of KHMDS or nBuLi, where two novel U(IV) complexes with or without P-P coupling were formed, respectively. The reversible P-P coupling in these complexes was observed in redox-induced reactions.

Reductive elimination of [AlH2]+ from a cationic Ga-Al dihydride.

Oxidative addition of TMEDA-supported [AlH2]+ to [{BDI}Ga] (BDI = {HC(C(CH3)N(2,6-iPr2-C6H3))2}) provides [{BDI}Ga(H)-Al(H)(tmeda)][B(C6H3-3,5-Me2)4] (TMEDA = N,N,N'N'-tetramethylethylenediamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an N-heterocyclic carbene or dissolving in THF.

Cationic strontium hydride complexes supported by an NNNN-type macrocycle.

A trinuclear strontium hydride [(Me4TACD)3Sr3(µ2-H)4(thf)][B(C6H3-3,5-Me2)4]2 (Me4TACD = 1,4,7,10-tetramethyltetraazacyclododecane) and a mixed calcium strontium hydride [(Me4TACD)2CaSr(µ-H)2(thf)][B(C6H3-3,5-Me2)4]2 were isolated by hydrogenolysis of cationic benzyl precursors. A solution of [(Me4TACD)2CaSr(µ-H)2(thf)][B(C6H3-3,5-Me2)4]2 shows hydride ligand exchange between calcium and strontium centers and higher affinity of the hydride ligand toward calcium.

C-N and C-H Activation of an N-Heterocyclic Carbene by Magnesium(II) Hydride and Magnesium(I) Complexes.

Reactions of the hindered N-heterocyclic carbene, :C{(MesNCH)2} (IMes; Mes = mesityl), with a series of ß-diketiminatomagnesium(II) hydride and dimagnesium(I) complexes were carried out at 80 °C. The reactions involving the magnesium hydrides, [{(ArNacnac)Mg(µ-H)}2] [ArNacnac = [(ArNCMe)2CH]-, where Ar = 2,6-diethylphenyl (Dep) or 2,6-diisopropylphenyl (Dip)], proceeded via activation of an exocyclic C-N bond of IMes, giving magnesium imidazolyl compounds [(ArNacnac)Mg(µ-H)(µ-Imid)Mg(ArNacnac)] (Imid = [NC2H2N(Mes)C]-) and mesitylene. A low-yield IMes methyl C-H activation product, [(DepNacnac)Mg(IMes-H)], was also obtained, via H2 elimination, from the reaction between IMes and [{(DepNacnac)Mg(µ-H)}2]. Reactions between IMes and dimagnesium(I) compounds [{(ArNacnac)Mg}2] [Ar = 2,6-dimethylphenyl (Xyl) or Mes] afforded isostructural C-H activation products [(ArNacnac)Mg(IMes-H)] but in higher yields. Density functional theory calculations suggest that the reactions do not progress via stable adduct complex intermediates, which are sterically inaccessible.

Scandium-Terminal Boronylphosphinidene Complex.

The first isolation and structural characterization of a rare-earth metal-terminal imido complex were reported in 2010, but a rare-earth metal-terminal phosphinidene complex is still absent, to date. Herein, we report the synthesis and structure of the first example of a rare-earth-terminal phosphinidene complex, namely the scandium boronylphosphinidene complex. Single-crystal X-ray diffraction shows that the complex has a much shorter Sc-P bond length as compared to that in a related scandium boronylphosphido complex, 2.381(1) Å vs 2.564(1) Å. DFT calculations indicate the presence of a strong Sc-P π interaction in this complex, which is in striking contrast to the weak interaction found in the phosphido complex. A preliminary reactivity study demonstrates that the scandium-terminal boronylphosphinidene complex behaves as a nucleophilic phosphinidene complex.

σ or π? Bonding interactions in a series of rhenium metallotetrylenes.

Salt metathesis reactions between a low-valent rhenium(i) complex, Na[Re(η5-Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-ß-diketiminate), and a series of amidinate-supported tetrylenes of the form ECl[PhC(NtBu)2] (E = Si, Ge, Sn) led to rhenium metallotetrylenes Re(E[PhC(NtBu)2])(η5-Cp)(BDI) (E = Si (1a), Ge (2), Sn (4)) with varying extents of Re-E multiple bonding. Whereas the rhenium-stannylene 4 adopts a σ-metallotetrylene arrangement featuring a Re-E single bond, the rhenium-silylene (1a) and -germylene (2) both engage in π-interactions to form short Re-E multiple bonds. Temperature was found to play a crucial role in reactions between Na[Re(η5-Cp)(BDI)] and SiCl[PhC(NtBu)2], as manipulation of reaction conditions led to isolation of an unusual rhenium-silane, (BDI)Re(µ-η5:η1-C5H4)(SiH[PhC(NtBu)2]) (1b) and a dinitrogen bridged rhenium-silylene, (η5-Cp)(BDI)Re(µ-N2)Si[PhC(NtBu)2] (1c), in addition to 1a. Finally, the reaction of Na[Re(η5-Cp)(BDI)] with GeCl2·dioxane led to a rare µ2-tetrelido complex, µ2-Ge[Re(η5-Cp)(BDI)]2 (3). Bonding interactions within these complexes are discussed through the lens of various spectroscopic, structural, and computational investigations.