A Lead-µ2-Tetrylide Complex with Osmium(IV) Terminal Components.

A bare lead atom is a σ-donor ligand capable of linearly bonding and stabilizing two units of a classical polyhydride complex, with a high-valent metal center. As a proof of concept, we have prepared and characterized the µ2-tetrylide complex (PiPr3)2H4Os═Pb═OsH4(PiPr3)2 in the reaction of OsH6(PiPr3)2 with Pb{N(SiMe3)2}2. Although the Pb-Os bonds exhibit electrostatic interaction, the main orbital interactions result from two dative σ bonds from the lead atom to the osmium centers. The latter also provide much weaker π-backdonations.

N,C,N-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties.

Precursors PtCl{κ3-N,C,N-[py-C6HMe2-py]} (1), PtCl{κ3-N,C,N-[py-O-C6H3-O-py]} (2), Pt(OH){κ3-N,C,N-[py-C6HMe2-py]} (3), and Pt(OH){κ3-N,C,N-[py-O-C6H3-O-py]} (4) were used to prepare d8-platinum bimetallic complexes. Precursors 1 and 2 react with AgBF4 and 7-azaindole (Haz) to give [Pt{κ3-N,C,N-[py-C6HMe2-py]}{κ1-N-[Haz]}]BF4 (5) and [Pt{κ3-N,C,N-[py-O-C6H3-O-py]}{κ1-N-[Haz]}]BF4 (6) and 3 and 4 with indolo[2,3-b]indole (H2ii) to generate Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-C6HMe2-py]} (7) and Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-O-C6H3-O-py]} (8). Subsequent addition of 3 and 4 to 5-7 affords bimetallic derivatives [{Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{µ-N,N-[az]}]BF4 (9), [{Pt[κ3-N,C,N-(py-O-C6H3-O-py)]}2{µ-N,N-[az]}]BF4 (10), and {Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{µ-N,N-[ii]} (11). X-ray structures of 9-11 reveal separations between the metals in sequence 9 (3.0515(4) Å) < 10 (3.2689(9) Å) < 11 (3.2949(2) Å). DFT calculations support σ overlap of the dz2 orbitals of platinum atoms, for 9 and 10. Accordingly, their absorption spectra show a MMLCT transition. Complex 9 is a red emitter. The excited state has 3MMLCT characteristics and a Pt-Pt separation of 2.763 Å. Complex 11 is a dual emitter in the red and NIR regions, in solid. Both excited states have a 3LC/LMCT characteristic and platinum-platinum separations of 3.290 and 3.202 Å. Intermediate 5 is a green emitter that achieves quantum yields close to unity, when diluted in PMMA and 1,2-dichloroethane at low concentrations.

Unequivocal Characterization of an Osmium Complex with a Terminal Sulfide Ligand and Its Transformation into Hydrosulfide and Methylsulfide.

Deprotonation of the thioamidate group of [OsH{κ2-N,S-[NHC(CH3)S]}(≡CPh)(IPr)(PiPr3)]OTf [1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3] results in the release of acetonitrile and formation of the terminal sulfide complex OsH(S)(≡CPh)(IPr)(PiPr3) (2), which has been transformed into the hydrosulfide [OsH(SH)(≡CPh)(IPr)(PiPr3)]OTf (3) and the methylsulfide [OsH(SMe)(≡CPh)(IPr)(PiPr3)]OTf (4) through protonation and methylation reactions, respectively. The structure, spectroscopic characteristics, and reactivity of these compounds are compared. Reactions of 3 and 4 with 2-hydroxypyridine and 2-mercaptopyridine afford [OsH{κ2-X,N-[X-py]}(≡CPh)(IPr)(PiPr3)]OTf [X = O (5), S(6)].

C-H, N-H, and O-H Bond Activations to Prepare Phosphorescent Hydride-Iridium(III)-Phosphine Emitters with Photocatalytic Achievement in C-C Coupling Reactions.

Complex IrH5(PiPr3)2 (1) activates two different σ-bonds of 3-phenoxy-1-phenylisoquinoline, 2-(1H-benzimidazol-2-yl)-6-phenylpyridine, 2-(1H-indol-2-yl)-6-phenylpyridine, 2-(2-hydroxyphenyl)-6-phenylpyridine, N-(2-hydroxyphenyl)-N'-phenylimidazolylidene, and 1,3-di(2-pyridyl)-4,6-dimethylbenzene to give IrH{κ3-C,N,C-[C6H4-isoqui-O-C6H4]}(PiPr3)2 (2), IrH{κ3-N,N,C-[NBzim-py-C6H4]}(PiPr3)2 (3), IrH{κ3-N,N,C-[Ind-py-C6H4]}(PiPr3)2 (4), IrH{κ3-C,N,O-[C6H4-py-C6H4O]}(PiPr3)2 (5), IrH{κ3-C,C,O-[C6H4-Im-C6H4O]}(PiPr3)2 (6), and IrH{κ3-N,C,C-[py-C6HMe2-C5H3N]}(PiPr3)2 (7), respectively. The activations are sequential, with the second generally being the slowest. Accordingly, dihydride intermediates IrH2{κ2-C,N-[C6H4-isoqui-O-C6H5]}(PiPr3)2 (2d), IrH2{κ2-N,N-[NBzim-py-C6H5]}(PiPr3)2 (3d), IrH2{κ2-N,N-[Ind-py-C6H5]}(PiPr3)2 (4d), and IrH2{κ2-N,C-[py-C6HMe2-py]}(PiPr3)2 (7d) were characterized spectroscopically. Complexes 3 and 5 are green phosphorescent emitters upon photoexcitation, exhibiting good absorption over a wide range of wavelengths, emission quantum yields about 0.70 in solution, long enough lifetimes (10-17 µs), and reversible electrochemical behavior. In agreement with these features, complex 3 promotes the photocatalytic α-amino C(sp3)-H arylation of N,N-dimethylaniline and N-phenylpiperidine with 1,4-dicyanobenzene and 4-cyanopyridine under blue LED light irradiation. The C-C coupling products are isolated in high yields with only 2 mol % of photocatalyst after 24 h.

Preparation, Aromaticity, and Bromination of Spiro Iridafurans.

Iridium centers of [Ir(µ-Cl)(C8H14)2]2 (1) activate the Cß(sp2)-H bond of benzylideneacetone to give [Ir(µ-Cl){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (2), which is the starting point for the preparation of the spiro iridafurans IrCl{κ2-C,O-[C(Ph)CHC(Me)O]}2(PiPr3) (3), [Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2(MeCN)2]BF4 (4), [Ir(µ-OH){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (5), Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-C,N-[C6MeH3-py]} (6), and Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acac]} (7). The five-membered rings are orthogonally arranged with the oxygen atoms in trans in an octahedral environment of the iridium atom. Spiro iridafurans are aromatic. The degree of aromaticity and the negative charge of the CH-carbon of the rings depend on ligand trans to the carbon directly attached to the metal. Aromaticity has been experimentally confirmed by bromination of iridafurans with N-bromosuccinimide (NBS). Reactions are sensitive to the degree of aromaticity of the ring and the negative charge of the attacked CH-carbon. Iridafurans can be selectively brominated, when different ligands lie trans to metalated carbons. Bromination of 3 occurs in the ring with the metalated carbon trans to chloride, whereas the bromination of 6 takes place in the ring with the metalated carbon trans to pyridyl. The first gives IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}(PiPr3) (8), which reacts with more NBS to form IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}2(PiPr3) (9). The second yields Ir{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}{κ2-C,N-[C6MeH3-py]} (10). The origin of the selectivity is kinetic, with the rate-determining step of the reaction being the NBS attack. The activation energy depends on the negative charge of the attacked atom; a higher negative charge allows for a lower activation energy. Accordingly, complex 7 undergoes bromination in the acetylacetonate ligand, giving Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acacBr]} (11).

Competition between N,C,N-Pincer and N,N-Chelate Ligands in Platinum(II).

Replacement of the chloride ligand of PtCl{κ3-N,C,N-[py-C6HR2-py]} (R = H (1), Me (2)) and PtCl{κ3-N,C,N-[py-O-C6H3-O-py]} (3) by hydroxido gives Pt(OH){κ3-N,C,N-[py-C6HR2-py]} (R = H (4), Me (5)) and Pt(OH){κ3-N,C,N-[py-O-C6H3-O-py]} (6). These compounds promote deprotonation of 3-(2-pyridyl)pyrazole, 3-(2-pyridyl)-5-methylpyrazole, 3-(2-pyridyl)-5-trifluoromethylpyrazole, and 2-(2-pyridyl)-3,5-bis(trifluoromethyl)pyrrole. The coordination of the anions generates square-planar derivatives, which in solution exist as a unique species or equilibria between isomers. Reactions of 4 and 5 with 3-(2-pyridyl)pyrazole and 3-(2-pyridyl)-5-methylpyrazole provide Pt{κ3-N,C,N-[py-C6HR2-py]}{κ1-N1-[R'pz-py]} (R = H; R' = H (7), Me (8). R = Me; R' = H (9), Me (10)), displaying κ1-N1-pyridylpyrazolate coordination. A 5-trifluoromethyl substituent causes N1-to-N2 slide. Thus, 3-(2-pyridyl)-5-trifluoromethylpyrazole affords equilibria between Pt{κ3-N,C,N-[py-C6HR2-py]}{κ1-N1-[CF3pz-py]} (R = H (11a), Me (12a)) and Pt{κ3-N,C,N-[py-C6HR2-py]}{κ1-N2-[CF3pz-py]} (R = H (11b), Me (12b)). 1,3-Bis(2-pyridyloxy)phenyl allows the chelating coordination of the incoming anions. Deprotonations of 3-(2-pyridyl)pyrazole and its substituted 5-methyl counterpart promoted by 6 lead to equilibria between Pt{κ3-N,C,N-[pyO-C6H3-Opy]}{κ1-N1-[R'pz-py]} (R' = H (13a), Me (14a)) with a κ-N1-pyridylpyrazolate anion, keeping the pincer coordination of the di(pyridyloxy)aryl ligand, and Pt{κ2-N,C-[pyO-C6H3(Opy)]}{κ2-N,N-[R'pz-py]} (R' = H (13c), Me (14c)) with two chelates. Under the same conditions, 3-(2-pyridyl)-5-trifluoromethylpyrazole generates the three possible isomers: Pt{κ3-N,C,N-[pyO-C6H3-Opy]}{κ1-N1-[CF3pz-py]} (15a), Pt{κ3-N,C,N-[pyO-C6H3-Opy]}{κ1-N2-[CF3pz-py]} (15b), and Pt{κ2-N,C-[pyO-C6H3(Opy)]}{κ2-N,N-[CF3pz-py]} (15c). The N1-pyrazolate atom produces a remote stabilizing effect on the chelating form, pyridylpyrazolates being better chelate ligands than pyridylpyrrolates. Accordingly, reactions of 4-6 with 2-(2-pyridyl)-3,5-bis(trifluoromethyl)pyrrole yield Pt{κ3-N,C,N-[py-C6HR2-py]}{κ1-N1-[(CF3)2C4(py)HN]} (R = H (16), Me (17)) or Pt{κ3-N,C,N-[pyO-C6H3-Opy]}{κ1-N1-[(CF3)2C4(py)HN]} (18), displaying κ1-N1-pyrrolate coordination. Complexes 7-10 are efficient green phosphorescent emitters (488-576 nm). In poly(methyl methacrylate) (PMMA) films and in dichloromethane, they experience self-quenching, due to molecular stacking. Aggregation occurs through aromatic π-π interactions, reinforced by weak platinum-platinum interactions.

Two Synthetic Tools to Deepen the Understanding of the Influence of Stereochemistry on the Properties of Iridium(III) Heteroleptic Emitters.

Two complementary procedures are presented to prepare cis-pyridyl-iridium(III) emitters of the class [3b+3b+3b'] with two orthometalated ligands of the 2-phenylpyridine type (3b) and a third ligand (3b'). They allowed to obtain four emitters of this class and to compare their properties with those of the trans-pyridyl isomers. The finding starts from IrH5(PiPr3)2, which reacts with 2-(p-tolyl)pyridine to give fac-[Ir{κ2-C,N-[C6MeH3-py]}3] with an almost quantitative yield. Stirring the latter in the appropriate amount of a saturated solution of HCl in toluene results in the cis-pyridyl adduct IrCl{κ2-C,N-[C6MeH3-py]}2{κ1-Cl-[Cl-H-py-C6MeH4]} stabilized with p-tolylpyridinium chloride, which can also be transformed into dimer cis-[Ir(µ-OH){κ2-C,N-[C6MeH3-py]}2]2. Adduct IrCl{κ2-C,N-[C6MeH3-py]}2{κ1-Cl-[Cl-H-py-C6MeH4]} directly generates cis-[Ir{κ2-C,N-[C6MeH3-py]}2{κ2-C,N-[C6H4-Isoqui]}] and cis-[Ir{κ2-C,N-[C6MeH3-py]}2{κ2-C,N-[C6H4-py]}] by transmetalation from Li[2-(isoquinolin-1-yl)-C6H4] and Li[py-2-C6H4]. Dimer cis-[Ir(µ-OH){κ2-C,N-[C6MeH3-py]}2]2 is also a useful starting complex when the precursor molecule of 3b' has a fairly acidic hydrogen atom, suitable for removal by hydroxide groups. Thus, its reactions with 2-picolinic acid and acetylacetone (Hacac) lead to cis-Ir{κ2-C,N-[C6MeH3-py]}2{κ2-O,N-[OC(O)-py]} and cis-Ir{κ2-C,N-[C6MeH3-py]}2{κ2-O,O-[acac]}. The stereochemistry of the emitter does not significantly influence the emission wavelengths. On the contrary, its efficiency is highly dependent on and associated with the stability of the isomer. The more stable isomer shows a higher quantum yield and color purity.

Ligand Design and Preparation, Photophysical Properties, and Device Performance of an Encapsulated-Type Pseudo-Tris(heteroleptic) Iridium(III) Emitter.

The organic molecule 2-(1-phenyl-1-(pyridin-2-yl)ethyl)-6-(3-(1-phenyl-1-(pyridin-2-yl)ethyl)phenyl)pyridine (H3L) has been designed, prepared, and employed to synthesize the encapsulated-type pseudo-tris(heteroleptic) iridium(III) derivative Ir(κ6-fac-C,C',C″-fac-N,N',N″-L). Its formation takes place as a result of the coordination of the heterocycles to the iridium center and the ortho-CH bond activation of the phenyl groups. Dimer [Ir(µ-Cl)(η4-COD)]2 is suitable for the preparation of this compound of class [Ir(9h)] (9h = 9-electron donor hexadentate ligand), but Ir(acac)3 is a more appropriate starting material. Reactions were carried out in 1-phenylethanol. In contrast to the latter, 2-ethoxyethanol promotes the metal carbonylation, inhibiting the full coordination of H3L. Complex Ir(κ6-fac-C,C',C″-fac-N,N',N″-L) is a phosphorescent emitter upon photoexcitation, which has been employed to fabricate four yellow emitting devices with 1931 CIE (x:y) ∼ (0.52:0.48) and a maximum wavelength at 576 nm. These devices display luminous efficacies, external quantum efficiencies, and power efficacies at 600 cd m-2, which lie in the ranges 21.4-31.3 cd A-1, 7.8-11.3%, and 10.2-14.1 lm W1-, respectively, depending on the device configuration.

Synthesis, Structure, and Photophysical Properties of Platinum(II) (N,C,N') Pincer Complexes Derived from Purine Nucleobases†.

The synthesis of a series of Pt{κ3-N,C,N'-[L]}X (X = Cl, RC≡C) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the N,C-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional N'-coordination point to the pincer complex. The purine N,C-fragment has two coordination positions with the metal (N1 and N7), but the formation of the platinum complexes is totally regioselective. Coordination through the N7 position leads to the thermodynamically favored [6.5]-Pt{κ3-N7,C,N'-[L]}X complexes. However, the coordination through the N1 position is preferred by the amino derivatives, leading to the isomeric kinetic [5.5]-Pt{κ3-N1,C,N'-[L]}X complexes. Extension of the reported methodology to complexes having both pincer and acetylide ligands derived from nucleosides allows the preparation of novel heteroleptic bis-nucleoside compounds that could be regarded as organometallic models of Pt-induced interstrand cross-link. Complexes having amine or pyridine arms are green phosphorescence emitters upon photoexcitation at low concentrations in CH2Cl2 solution and in poly(methyl methacrylate) (PMMA) films. They undergo self-quenching at high concentrations due to molecular aggregation. The presence of intermolecular π-π stacking and weak Pt···Pt interactions was also observed in the solid state by X-ray diffraction analysis.

Homogeneous catalysis with polyhydride complexes.

Roles of the hydrogen atoms attached to the metal center of transition metal polyhydride complexes, LnMHx (x ≥ 3), are analyzed for about forty types of organic reactions catalyzed by such class of species. Reactions involve nearly every main organic functional group and represent friendly environmental procedures of synthesis of relevant and necessary molecules in several areas ranging from energy and environment to medicine or pharmacology. Catalysts are mainly complexes of group 8 metals, along with rhenium and iridium, and manganese and cobalt to a lesser extent. Their MHx units can be formed by Kubas-type dihydrogen, elongated dihydrogen, or hydride ligands, which facilitate both the homolytic and heterolytic σ-bond activation reactions and hydrogen transfer processes from the metal center to unsaturated organic molecules. As a consequence of the ability of polyhydride complexes to activate σ-bonds, the vast majority of the reactions catalyzed by derivatives of this class involve at least one σ-bond activation elemental step, whereas two sequential ruptures of σ-bonds and the cross-coupling of the resulting fragments take place in a variety of reactions of C-H functionalization and hydrodefluorination. The hydrogen transfer processes usually generate highly unsaturated metal fragments, which are very reactive and extremely active in interesting C-C coupling reactions. Polyhydride complexes bearing Kubas-type dihydrogen ligands are the last intermediates in dehydrogenation processes, while they can be the first ones in hydrogenation reactions. Polyhydrides coordinating elongated dihydrogen ligands are acidic, while classical hydride complexes behave as Brønsted bases. The combination of the properties of both types of species in a catalytic cycle gives rise to interesting outer-sphere processes. The basic character of the classical hydride ligands also confers them the ability of cooperating in the coordination of acidic molecules such as boranes, which is of great relevance for reactions involving the activation of a B-H bond. Multiple bonds of unsaturated organic molecules also undergo insertion into the M-H bond of the catalysts. Such insertions are a key step in many processes.

Acetylides for the Preparation of Phosphorescent Iridium(III) Complexes: Iridaoxazoles and Their Transformation into Hydroxycarbenes and N,C(sp3),C(sp2),O-Tetradentate Ligands.

The preparation of three families of phosphorescent iridium(III) emitters, including iridaoxazole derivatives, hydroxycarbene compounds, and N,C(sp3),C(sp2),O-tetradentate containing complexes, has been performed starting from dimers cis-[Ir(µ2-η2-C≡CR){κ2-C,N-(MeC6H3-py)}2]2 (R = tBu (1a), Ph (1b)). Reactions of 1a with benzamide, acetamide, phenylacetamide, and trifluoroacetamide lead to the iridaoxazole derivatives Ir{κ2-C,O-[C(CH2tBu)NC(R)O]}{κ2-C,N-(MeC6H3-py)}2 (R = Ph (2), Me (3), CH2Ph (4), CF3 (5)) with a fac disposition of carbons and heteroatoms around the metal center. In 2-methyltetrahydrofuran and dichloromethane, water promotes the C-N rupture of the IrC-N bond of the iridaoxazole ring of 3-5 to form amidate-iridium(III)-hydroxycarbene derivatives Ir{κ1-N-[NHC(R)O]}{κ2-C,N-(MeC6H3-py)}2{═C(CH2tBu)OH} (R = Me (6), CH2Ph (7), CF3 (8)). In contrast to 1a, dimer 1b reacts with benzamide and acetamide to give Ir{κ4-N,C,C',O-[py-MeC6H3-C(CH2-C6H4)NHC(R)O]}{κ2-C,N-(MeC6H3-py)}(R = Ph (9), Me (10)), which bear a N,C(sp3),C(sp2),O-tetradentate ligand resulting from a triple coupling (an alkynyl ligand, an amide, and a coordinated aryl group) and a C-H bond activation at the metal coordination sphere. Complexes 2-4 and 6-10 are emissive upon photoexcitation, in orange (2-4), green (6-8), and yellow (9 and 10) regions, with quantum yields between low and moderate (0.01-0.50) and short lifetimes (0.2-9.0 µs).

Alkynyl Ligands as Building Blocks for the Preparation of Phosphorescent Iridium(III) Emitters: Alternative Synthetic Precursors and Procedures.

Alkynyl ligands stabilize dimers [Ir(µ-X)(3b)2]2 with a cis disposition of the heterocycles of the 3b ligands, in contrast to chloride. Thus, the complexes of this class─cis-[Ir(µ2-η2-C≡CPh){κ2-C,N-(C6H4-Isoqui)}2]2 (Isoqui = isoquinoline) and cis-[Ir(µ2-η2-C≡CR){κ2-C,N-(MeC6H3-py)}2]2 (R = Ph, tBu)─have been prepared in high yields, starting from the dihydroxo-bridged dimers trans-[Ir(µ-OH){κ2-C,N-(C6H4-Isoqui)}2]2 and trans-[Ir(µ-OH){κ2-C,N-(MeC6H3-py)}2]2 and terminal alkynes. Subsequently, the acetylide ligands have been employed as building blocks to prepare the orange and green iridium(III) phosphorescent emitters, Ir{κ2-C,N-[C(CH2Ph)Npy]}{κ2-C,N-(C6H4-Isoqui)}2 and Ir{κ2-C,N-[C(CH2R)Npy]}{κ2-C,N-(MeC6H3-py)}2 (R = Ph, tBu), respectively, with an octahedral structure of fac carbon and nitrogen atoms. The green emitter Ir{κ2-C,N-[C(CH2tBu)Npy]}{κ2-C,N-(MeC6H3-py)}2 reaches 100% of quantum yield in both the poly(methyl methacrylate) (PMMA) film and 2-MeTHF at room temperature. In organic light-emitting diode (OLED) devices, it demonstrates very saturated green emission at a peak wavelength of 500 nm, with an external quantum efficiency (EQE) of over 12% or luminous efficacy of 30.7 cd/A.

Metathesis between E-C(spn ) and H-C(sp3 ) σ-Bonds (E=Si, Ge; n=2, 3) on an Osmium-Polyhydride.

The silylation of a phosphine of OsH6 (Pi Pr3 )2 is performed via net-metathesis between Si-C(spn ) and H-C(sp3 ) σ-bonds (n=2, 3). Complex OsH6 (Pi Pr3 )2 activates the Si-H bond of Et3 SiH and Ph3 SiH to give OsH5 (SiR3 )(Pi Pr3 )2 , which yield OsH4 {κ1 -P,η2 -SiH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) and R-H (R=Et, Ph), by displacement of a silyl substituent with a methyl group of a phosphine. Such displacement is a first-order process, with activation entropy consistent with a rate determining step occurring via a highly ordered transition state. It displays selectivity, releasing the hydrocarbon resulting from the rupture of the weakest Si-substituent bond, when the silyl ligand bears different substituents. Accordingly, reactions of OsH6 (Pi Pr3 )2 with dimethylphenylsilane, and 1,1,1,3,5,5,5-heptamethyltrisiloxane afford OsH5 (SiR2 R')(Pi Pr3 )2 , which evolve into OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) (R=Me, OSiMe3 ) and R'-H (R'=Ph, Me). Exchange reaction is extended to Et3 GeH. The latter reacts with OsH6 (Pi Pr3 )2 to give OsH5 (GeEt3 )(Pi Pr3 )2 , which loses ethane to form OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 GeEt2 H]}(Pi Pr3 ).

Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism.

The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.

Electronic Communication in Binuclear Osmium- and Iridium-Polyhydrides.

Reactions of polyhydrides OsH6(PiPr3)2 (1) and IrH5(PiPr3)2 (2) with rollover cyclometalated hydride complexes have been investigated in order to explore the influence of a metal center on the MHn unit of the other in mixed valence binuclear polyhydrides. Hexahydride 1 activates an ortho-CH bond of the heterocyclic moiety of the trihydride metal-ligand compounds OsH3{κ2-C,N-[C5RH2N-py]}(PiPr3)2 (R = H (3), Me (4), Ph (5)). Reactions of 3 and 4 lead to the hexahydrides (PiPr3)2H3Os{µ-[κ2-C,N-[C5RH2N-C5H3N]-N,C-κ2]}OsH3(PiPr3)2 (R = H (6), Me (7)), whereas 5 gives the pentahydride (PiPr3)2H3Os{µ-[κ2-C,N-[C5H3N-C5(C6H4)H2N]-C,N,C-κ3]}OsH2(PiPr3)2 (8). Pentahydride 2 promotes C-H bond activation of 3 and the iridium-dihydride IrH2{κ2-C,N-[C5H3N-py]}(PiPr3)2 (9) to afford the heterobinuclear pentahydride (PiPr3)2H3Os{µ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (10) and the homobinuclear tetrahydride (PiPr3)2H2Ir{µ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (11), respectively. Complexes 6-8 and 11 display HOMO delocalization throughout the metal-heterocycle-metal skeleton. Their sequential oxidation generates mono- and diradicals, which exhibit intervalence charge transfer transitions. This notable ability allows the tuning of the strength of the hydrogen-hydrogen and metal-hydrogen interactions within the MHn units.

Alternative Conceptual Approach to the Design of Bifunctional Catalysts: An Osmium Germylene System for the Dehydrogenation of Formic Acid.

The reaction of the hexahydride OsH6(PiPr3)2 with a P,Ge,P-germylene-diphosphine affords an osmium tetrahydride derivative bearing a Ge,P-chelate, which arises from the hydrogenolysis of a P-C(sp3) bond. This Os(IV)-Ge(II) compound is a pioneering example of a bifunctional catalyst based on the coordination of a σ-donor acid, which is active in the dehydrogenation of formic acid to H2 and CO2. The kinetics of the dehydrogenation, the characterization of the resting state of the catalysis, and DFT calculations point out that the hydrogen formation (the fast stage) exclusively occurs on the coordination sphere of the basic metal center, whereas both the metal center and the σ-donor Lewis acid cooperatively participate in the CO2 release (the rate-determining step). During the process, the formate group pivots around the germanium to approach its hydrogen atom to the osmium center, which allows its transfer to the metal and the CO2 release.

Pseudo-Tris(heteroleptic) Red Phosphorescent Iridium(III) Complexes Bearing a Dianionic C,N,C',N'-Tetradentate Ligand.

1-Phenyl-3-(1-phenyl-1-(pyridin-2-yl)ethyl)isoquinoline (H2MeL) has been prepared by Pd(N-XantPhos)-catalyzed "deprotonative cross-coupling processes" to synthesize new phosphorescent red iridium(III) emitters (601-732 nm), including the carbonyl derivative Ir(κ4-cis-C,C'-cis-N,N'-MeL)Cl(CO) and the acetylacetonate compound Ir(κ4-cis-C,C'-cis-N,N'-MeL)(acac). The tetradentate 6e-donor ligand (6tt') of these complexes is formed by two different bidentate units, namely, an orthometalated 2-phenylisoquinoline and an orthometalated 2-benzylpyridine. The link between the bidentate units reduces the number of possible stereoisomers of the structures [6tt' + 3b] (3b = bidentate 3e-donor ligand), with respect to a [3b + 3b' + 3b″] emitter containing three free bidentate units, and it permits a noticeable stereocontrol. Thus, the isomers fac-Ir(κ4-cis-C,C'-cis-N,N'-MeL){κ2-C,N-(C6H4-py)}, mer-Ir(κ4-cis-C,C'-cis-N,N'-MeL){κ2-C,N-(C6H3R-py)}, and mer-Ir(κ4-trans-C,C'-cis-N,N'-MeL){κ2-C,N-(C6HR-py)} (R = H, Me) have also been selectively obtained. The new emitters display short lifetimes (0.7-4.6 µs) and quantum yields in a doped poly(methyl methacrylate) film at 5 wt % and 2-methyltetrahydrofuran at room temperature between 0.08 and 0.58. The acetylacetonate complex Ir(κ4-cis-C,C'-cis-N,N'-MeL)(acac) has been used as a dopant for a red PhOLED device with an electroluminescence λmax of 672 nm and an external quantum efficiency of 3.4% at 10 mA/cm2.

Kinetic Analysis and Sequencing of Si-H and C-H Bond Activation Reactions: Direct Silylation of Arenes Catalyzed by an Iridium-Polyhydride.

The saturated trihydride IrH3{κ3-P,O,P-[xant(PiPr2)2]} (1; xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) coordinates the Si-H bond of triethylsilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, and triphenylsilane to give the σ-complexes IrH3(η2-H-SiR3){κ2-cis-P,P-[xant(PiPr2)2]}, which evolve to the dihydride-silyl derivatives IrH2(SiR3){κ3-P,O,P-[xant(PiPr2)2]} (SiR3 = SiEt3 (2), SiMe(OSiMe3)2 (3), SiPh3 (4)) by means of the oxidative addition of the coordinated bond and the subsequent reductive elimination of H2. Complexes 2-4 activate a C-H bond of symmetrically and asymmetrically substituted arenes to form silylated arenes and to regenerate 1. This sequence of reactions defines a cycle for the catalytic direct C-H silylation of arenes. Stoichiometric isotopic experiments and the kinetic analysis of the transformations demonstrate that the C-H bond rupture is the rate-determining step of the catalysis. As a consequence, the selectivity of the silylation of substituted arenes is generally governed by ligand-substrate steric interactions.

Direct C-H Borylation of Arenes Catalyzed by Saturated Hydride-Boryl-Iridium-POP Complexes: Kinetic Analysis of the Elemental Steps.

The saturated trihydride IrH3 {κ3 -P,O,P-[xant(PiPr2 )2 ]} (1; xant(PiPr2 )2 =9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) activates the B-H bond of two molecules of pinacolborane (HBpin) to give H2 , the hydride-boryl derivatives IrH2 (Bpin){κ3 -P,O,P-[xant(PiPr2 )2 ]} (2) and IrH(Bpin)2 {κ3 -P,O,P-[xant(PiPr2 )2 ]} (3) in a sequential manner. Complex 3 activates a C-H bond of two molecules of benzene to form PhBpin and regenerates 2 and 1, also in a sequential manner. Thus, complexes 1, 2, and 3 define two cycles for the catalytic direct C-H borylation of arenes with HBpin, which have dihydride 2 as a common intermediate. C-H bond activation of the arenes is the rate-determining step of both cycles, as the C-H oxidative addition to 3 is faster than to 2. The results from a kinetic study of the reactions of 1 and 2 with HBpin support a cooperative function of the hydride ligands in the B-H bond activation. The addition of the boron atom of the borane to a hydride facilitates the coordination of the B-H bond through the formation of κ1 - and κ2 -dihydrideborate intermediates.

A General Rhodium Catalyst for the Deuteration of Boranes and Hydrides of the Group 14 Elements.

Pinacolborane, catecholborane, triethylsilane, triphenylsilane, dimethylphenylsilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, triethylgermane, triphenylgermane, and triphenylstannane deuterated at the heteroatom position have been catalytically prepared in 50-70% isolated yield, through H/D exchange between the D2 molecule and the respective boranes and hydrides of the group 14 elements, in the presence of the rhodium(I)-monohydride catalyst precursor RhH{κ3-P,O,P-[xant(PiPr2)2]} (xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene).