Correction: Iridium-(κ2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance.

Correction for 'Iridium-(κ2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance' by Alejandra Gomez-España et al., Dalton Trans., 2023, 52, 6722-6729, https://doi.org/10.1039/d3dt00744h.

Iridium-(κ2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance.

The iridium(III) complexes [Ir(H)(Cl)(κ2-NSitBu2)(κ2-bipyMe2)] (2) and [Ir(H)(OTf)(κ2-NSitBu2)(κ2-bipyMe2)] (3) (NSitBu2 = {4-methylpyridine-2-yloxy}ditertbutylsilyl) have been synthesized and characterized including X-ray studies of 3. A comparative study of the catalytic activity of complexes 2, 3, [Ir(H)(OTf)(κ2-NSitBu2)(coe)] (4), and [Ir(H)(OTf)(κ2-NSitBu2)(PCy3)] (5) (0.1 mol%) as catalysts precursors for the solventless formic acid dehydrogenation (FADH) in the presence of Et3N (40 mol%) at 353 K has been performed. The highest activity (TOF5 min ≈ 3260 h-1) has been obtained with 3 at 373 K. However, at that temperature the FTIR spectra show traces of CO together with the desired products (H2 and CO2). Thus, the best performance was achieved at 353 K (TOF5 min ≈ 1210 h-1 and no observable CO). Kinetic studies at variable temperature show that the activation energy of the 3-catalyzed FADH process is 16.76 kcal mol-1. Kinetic isotopic effect (5 min) values of 1.6, 4.5, and 4.2 were obtained for the 3-catalyzed dehydrogenation of HCOOD, DCOOH, and DCOOD, respectively, at 353 K. The strong KIE found for DCOOH and DCOOD evidenced that the hydride transfer from the C-H bond of formic acid to the metal is the rate-determining step of the process.

Correction: Iridium-(κ2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance.

Correction for 'Iridium-(κ2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance' by Alejandra Gomez-España et al., Dalton Trans., 2023, https://doi.org/10.1039/d3dt00744h.

Mechanism Insights into the Iridium(III)- and B(C6F5)3-Catalyzed Reduction of CO2 to the Formaldehyde Level with Tertiary Silanes.

The catalytic system [Ir(CF3CO2)(κ2-NSiMe)2] [1; NSiMe = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C6F5)3 promotes the selective reduction of CO2 with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that species [Ir(CF3COO-B(C6F5)3)(κ2-NSiMe)2] (3), [Ir(κ2-NSiMe)2][HB(C6F5)3] (4), and [Ir(HCOO-B(C6F5)3)(κ2-NSiMe)2] (5) are intermediates of the catalytic process. The structure of 3 has been determined by X-ray diffraction methods. Theoretical calculations show that the rate-limiting step for the 1/B(C6F5)3-catalyzed hydrosilylation of CO2 to bis(silyl)acetal is a boron-promoted Si-H bond cleavage via an iridium silylacetal borane adduct.

Synthesis and Characterization of Ir-(κ2-NSi) Species Active toward the Solventless Hydrolysis of HSiMe(OSiMe3)2.

The reaction of [IrH(Cl)(κ2-NSitBu2)(coe)] (1) with 1 equiv of PCy3 (or PHtBu2) gives the species [IrH(Cl)(κ2-NSitBu2)(L)] (L = PCy3, 2a; PHtBu2, 2b), which reacts with 1 equiv of AgOTf to afford [IrH(OTf)(κ2-NSitBu2)(L)] (L = PCy3, 3a and PHtBu2, 3b). Complexes 2a, 2b, 3a, and 3b have been characterized by means of NMR spectroscopy and HR-MS. The solid-state structures of complexes 2a, 2b, and 3a have been determined by X-ray diffraction studies. The reversible coordination of water to 3a, 3b, and 4 to afford the corresponding adduct [IrH(OTf)(κ2-NSitBu2)(L)(H2O)] (L = PCy3, 3a-H2O; PHtBu2, 3b-H2O; coe, 4-H2O) has been demonstrated spectroscopically by NMR studies. The structure of complexes 3b-H2O and 4-H2O have been determined by X-ray diffraction studies. Computational analyses of the interaction between neutral [NSitBu2]• and [Ir(H)L(X)]• fragments in Ir-NSitBu2 species confirm the electron-sharing nature of the Ir-Si bond and the significant role of electrostatics in the interaction between the transition metal fragment and the κ2-NSitBu2 ligand. The activity of Ir-(κ2-NSitBu2) species as catalysts for the hydrolysis of HSiMe(OSiMe3)2 depends on the nature of the ancillary ligands. Thus, while the triflate derivatives are active, the related chloride species show no activity. The best catalytic performance has been obtained when using complexes 3a, with triflate and PCy3 ligands, as a catalyst precursor, which allows the selective obtention of the corresponding silanol.

Dehydrogenation of formic acid using iridium-NSi species as catalyst precursors.

Using a low loading of the iridium(III) complexes [Ir(CF3SO3)(κ2-NSiiPr)2] (1) (NSiiPr = (4-methylpyridin-2-yloxy)diisopropylsilyl) and [{Ir(κ2-NSiMe)2}2(µ-CF3SO3)2] (2) (NSiMe = (4-methylpyridin-2-yloxy)dimethylsilyl) in the presence of Et3N, it has been possible to achieve the solventless selective dehydrogenation of formic acid. The best catalytic performance (TOF5 min ≈ 2900 h-1) has been achieved with 2 (0.1 mol%) and Et3N (40 mol% to FA) at 373 K. Kinetic studies at variable temperatures show that the activation energy of the 2-catalyzed process at 353 K is 22.8 ± 0.8 kcal mol-1. KIE values of 1.33, 2.86, and 3.33 were obtained for the 2-catalyzed dehydrogenation of HCOOD, DCOOH, and DCOOD, respectively, in the presence of 10 mol% of Et3N at 353 K. These data show that the activation of the C-H bond of FA is the rate-determining step of the process. A DFT mechanistic study for the catalytic cycle involving hydride abstraction from the formate anion by the metal, assisted by a molecule of formic acid, and heterolytic H2 formation has been performed. Moreover, the presence of Ir-formate intermediates was identified by means of NMR studies of the catalytic reactions in thf-d8 at 323 K. In all the cases, the decomposition of the catalyst to give unactive crystalline iridium NPs was observed.

Origin of the Ir-Si bond shortening in Ir-NSiN complexes.

The Ir-Si bond distances reported for Ir-(fac-κ3-NSiNOPy) and Ir-(fac-κ3-NSiN4MeOPy) species (NSiNOPy = bis(pyridine-2-yloxy)methylsilyl and NSiN4MeOPy = bis(4-methyl-pyridine-2-yloxy)methylsily) are in the range of 2.220-2.235 Å. These values are in the lowest limit of the Ir-Si bond distances found in the Cambridge Structural Database (CSD). To understand the origin of such remarkable shortening, a computational study of the bonding situation of representative examples of Ir-(fac-κ3-NSiN) species has been carried out. It is found that the Ir-Si bond can be described as an electron-sharing (i.e. covalent) bond. Despite that, this bond is highly polarized and as a result, the contribution of the electrostatic attractions to the bonding is rather significant. Indeed, there exists a linear relationship (R2 = 0.97) between the Ir-Si bond distance and the extent of the computed electrostatic interactions, which indicates that the ionic contribution to the bonding is mainly responsible for the observed Ir-Si bond shortening.

2-Pyridone-stabilized iridium silylene/silyl complexes: structure and QTAIM analysis.

Iridium(iii) complexes of the general formula [Ir(X)(κ2-NSiiPr2)2] (NSiiPr2 = (4-methyl-pyridine-2-yloxy)diisopropylsilyl; X = Cl, 3; CF3SO3, 5; CF3CO2, 6) have been prepared and fully characterized, including X-ray diffraction studies and theoretical calculations. The presence of isopropyl substituents at the silicon atom favours the monomeric structure found in complexes 3 and 5. The short Ir-Si bond distances (2.25-2.28 Å) indicate some degree of base-stabilized silylene character of the Ir-Si bond in 3, 5 and 6 assisted by the 2-pyridone moiety. However, the shortening of these Ir-Si bonds might be a consequence of the constrained 2-pyridone geometry, and consequently the silyl character of these bonds can not be excluded. A DFT theoretical study on the nature of the Ir-Si bonds has been performed for complex 3 as well as for four other iridium complexes finding representative examples of different bonding situations between Ir and Si atoms: silylene, base-assisted silylene (both with an anionic base and with a neutral base), and silyl bonds, using the topological properties of the electron charge density. The results of these studies show that the Ir-Si bonds in Ir-NSiiPr2 complexes can be considered as an intermediate between the base-stabilized silylene and silyl cases, and therefore they have been proposed as 2-pyridone-stabilized iridium silylene/silyl bonds.

Unprecedent formation of methylsilylcarbonates from iridium-catalyzed reduction of CO2 with hydrosilanes.

The iridium complex [Ir(µ-CF3SO3)(κ2-NSiMe2)2]2 (3) (NSiMe2 = {4-methylpyridine-2-yloxy}dimethylsilyl) has been prepared by reaction of [Ir(µ-Cl)(κ2-NSiMe2)2]2 (1) with two equivalents of AgCF3SO3. The solid structure of 3 evidenced its dinuclear nature, being a rare example of an iridium species with triflate groups acting as bridges. The 3-catalyzed reduction of CO2 with HSiMe(OSiMe3)2 affords a mixture of the corresponding silylformate and methoxysilane together with the silylcarbonate CH3OCO2SiMe(OSiMe3)2 (4a). This is the first time that the formation of silylcarbonates has been observed from the catalytic reduction of CO2 with silanes. Analogous behaviour has been observed when HSiMe2Ph and HSiMePh2 were used as reductants.

Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexes.

The reaction of (4-methyl-pyridin-2-iloxy)ditertbutylsilane (NSitBu-H, 1) with [IrCl(coe)2]2 affords the iridium(iii) complex [Ir(H)(Cl)(κ2-NSitBu)(coe)] (2), which has been fully characterized including X-ray diffraction studies. The reaction of 2 with AgCF3SO3 leads to the formation of species [Ir(H)(CF3SO3)(κ2-NSitBu)(coe)] (3). The iridium complexes 2 and 3 are effective catalysts for the reduction of formamides with HSiMe2Ph. The selectivity of the reduction process depends on the catalyst. Thus, by using complex 2, with a chloride ancillary ligand, it has been possible to selectively obtain the corresponding O-silylated hemiaminal by reaction of formamides with one equivalent of HSiMe2Ph, while complex 3, with a triflate ligand instead of chloride, catalyzed the selective reduction of formamides to the corresponding methylamine.

Synthesis and reactivity at the Ir-MeTpm platform: from κ1-N coordination to κ3-N-based organometallic chemistry.

Reaction of [Ir(µ-Cl)(COE)2]2 (COE = cis-cyclooctene) with tris(3,5-dimethylpyrazol-1-yl)methane (MeTpm) affords [IrCl(κ1-N-MeTpm)(COD)] (1) (COD = 1,5-cyclooctadiene). The formation of 1 implies the transfer dehydrogenation of a COE ligand to give COD and COA (cyclooctane). A mechanistic proposal based on DFT calculations that explains this iridium promoted process has been disclosed. Additionally, reactivity studies have allowed the preparation and characterization, including determination of the molecular structures of a number of iridium complexes with the MeTpm ligand in κ1, κ2 or κ3-N coordination modes. Moreover, the first example of an Ir-cyclooctyl complex featuring hydride and carbonyl ligands, whose solid state structure has been determined by X-ray diffraction methods, is reported.

Mechanistic Insights on the Reduction of CO2 to Silylformates Catalyzed by Ir-NSiN Species.

The hydrosilylation of CO2 with different silanes such as HSiEt3 , HSiMe2 Ph, HSiMePh2 , HSiMe(OSiMe3 )2 , and HSi(OSiMe3 )3 in the presence of catalytic ammounts of the iridium(III) complex [Ir(H)(CF3 CO2 )(NSiN*)(coe)] (1; NSiN*=fac-bis-(4-methylpyridine-2-yloxy); coe=cis-cyclooctene) has been comparatively studied. The activity of the hydrosilylation catalytic system based on 1 depends on the nature of the reducing agent, where HSiMe(OSiMe3 )2 has proven to be the most active. The aforementioned reactions were found to be highly selective toward the formation of the corresponding silylformate. It has been found that using 1 as catalyst precursor above 328 K decreases the activity through a thermally competitive mechanistic pathway. Indeed, the reduction of the ancillary trifluoroacetate ligand to give the corresponding silylether CF3 CH2 OSiR3 has been observed. Moreover, mechanistic studies for the 1-catalyzed CO2 -hydrosilylation reaction based on experimental and theoretical studies suggest that 1 prefers an inner-sphere mechanism for the CO2 reduction, whereas the closely related [Ir(H)(CF3 SO3 )(NSiN)(coe)] catalyst, bearing a triflate instead of trifluoroacetate ligand, follows an outer-sphere mechanism.

Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers.

A series of rhodium-NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3 )] (Cy=cyclohexane) and [Rh(H)(CF3 SO3 )(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3 SO3 )(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3 SO3 )(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si-H bond by a metal-ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether.

Catalytic hydrodechlorination of benzyl chloride promoted by Rh-N-heterocyclic carbene catalysts.

The rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2 )3 Si(OiPr)3 )] [COD=cyclooctadiene; R=2,6-diisopropylphenyl (1 a); n-butyl (1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation of toluene. However, in presence of a stoichiometric amount of potassium tert-butoxide (KtBuO) the formation of mixtures containing toluene together with 17-19 mol % of the C--C homocoupling product, namely PhCH2 CH2 Ph, is observed. A mechanism proposal based on experimental insights and theoretical calculations at the DFT level that allows explanation of the experimental findings is included. Moreover, the heterogeneous catalytic system based on catalyst 1 a supported on MCM-41 has been demonstrated to be effective for the solvent-free hydrodechlorination of benzyl chloride using HSiEt3 and HSiMe(OSiMe3 )2 .

An alternative mechanistic paradigm for the ß-Z hydrosilylation of terminal alkynes: the role of acetone as a silane shuttle.

The ß-Z selectivity in the hydrosilylation of terminal alkynes has been hitherto explained by introduction of isomerisation steps in classical mechanisms. DFT calculations and experimental observations on the system [M(I)2{κ-C,C,O,O-(bis-NHC)}]BF4 (M=Ir (3a), Rh (3b); bis-NHC=methylenebis(N-2-methoxyethyl)imidazole-2-ylidene) support a new mechanism, alternative to classical postulations, based on an outer-sphere model. Heterolytic splitting of the silane molecule by the metal centre and acetone (solvent) affords a metal hydride and the oxocarbenium ion [R3Si-O(CH3)2](+), which reacts with the corresponding alkyne in solution to give the silylation product [R3Si-CH=C-R](+). Thus, acetone acts as a silane shuttle by transferring the silyl moiety from the silane to the alkyne. Finally, nucleophilic attack of the hydrido ligand over [R3Si-CH=C-R](+) affords selectively the ß-(Z)-vinylsilane. The ß-Z selectivity is explained on the grounds of the steric interaction between the silyl moiety and the ligand system resulting from the geometry of the approach that leads to ß-(E)-vinylsilanes.

A synthon for a 14-electron Ir(III) species: catalyst for highly selective ß-(Z) hydrosilylation of terminal alkynes.

A synthon for a 14-electron Ir(III) species is described. The geometrical control exerted by the ligand system over the Ir-alkenyl intermediate in hydrosilylation of terminal alkynes precludes formation of the more thermodynamically stable ß-(E)-vinylsilane, thus affording the ß-(Z) isomer in excellent yields.

Borinium cations as sigma-B-H ligands in osmium complexes.

The complex OsH(2)Cl(2)(P(i)Pr(3))(2) reacts with pinacolborane, Me(2)NH-BH(3), and (t)BuNH(2)-BH(3) to give the complexes OsH(2)Cl{eta(2)-HBOC(CH(3))(2)C(CH(3))(2)OBpin}(P(i)Pr(3))(2) and OsH(2)Cl(eta(2)-HBNR(1)R(2))(P(i)Pr(3))(2) (R(1) = R(2) = Me; R(1) = H, R(2) = (t)Bu) containing monosubstituted alkoxy- and amidoborinium cations coordinated as sigma-B-H ligands. The process is proposed to take place via the electrophilic 14-valence-electron fragment OsHCl(P(i)Pr(3))(2), which promotes hydride transfer from the corresponding borane to the osmium atom.

Stabilization of NH tautomers of quinolines by osmium and ruthenium.

Complexes OsH2Cl2(PiPr3)2 and RuH2Cl2(PiPr3)2 promote the tautomerization of quinoline and 8-methylquinoline to NH tautomers, which lie about 44 kcal.mol-1 above the usual CH tautomers. The NH tautomers are stabilized by coordination to the metal center and by means of a Cl...HN interaction. As a consequence, the six-coordinate elongated dihydrogen complexes OsCl2{kappa-C2-(HNC9H5R)}(eta2-H2)(PiPr3)2, the five-coordinate derivatives RuCl2{kappa-C2-(HNC9H5R)}(PiPr3)2, and the six-coordinate dihydrogen compounds RuCl2{kappa-C2-(HNC9H5R)}(eta2-H2)(PiPr3)2 (R = H, Me) have been isolated and characterized.

C-H bond activation and subsequent C-C bond formation promoted by osmium: 2-vinylpyridine-acetylene couplings.

Complex OsH2Cl2(PiPr3)2 promotes the C-H activation of 2-vinylpyridine and subsequently couples the activated substrate with a second 2-vinylpyridine and two acetylene molecules. In the absence of 2-vinylpyridine, the activated substrate is coupled with an acetylene unit to afford a 2-butadienylpyridine derivative.