Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines.

The low-electron count, air-stable, platinum complexes [Pt(ItBu')(ItBu)][BArF] (C1) (ItBu=1,3-di-tert-butylimidazol-2-ylidene), [Pt(SiPh)3(ItBuiPr)2][BArF] (C2) (ItBuiPr=1-tert-butyl-3-iso-propylimidazol-2-ylidene), [Pt(SiPh)3(ItBuMe)2][BArF] (C3), [Pt(GePh3)(ItBuiPr)2][BArF] (C4), [Pt(GePh)3(ItBuMe)2][BArF] (C5) and [Pt(GeEt)3(ItBuMe)2][BArF] (C6) (ItBuMe=1-tert-butyl-3-methylimidazol-2-ylidene) are efficient catalysts (particularly the germyl derivatives) in both the silylative dehydrocoupling and hydrosilylation of electron rich alkenes derived from enamines. The steric hindrance exerted by the NHC ligand plays an important role in the selectivity of the reaction. Thus, bulky ligands are selective towards the silylative dehydrocoupling process whereas less sterically hindered promote the selective hydrosilylation reaction. The latter is, in addition, regioselective towards the ß-carbon atom of both internal and terminal enamines, leading to ß-aminosilanes. Moreover, the syn stereochemistry of the amino and silyl groups implies an anti Si-H bond addition across the double bond. All these facts point to a mechanistic picture that, according to experimental and computational studies, involves a non-classical hydrosilylation process through an outer-sphere mechanism in which a formal nucleophilic addition of the enamine to the silicon atom of a platinum σ-SiH complex is the key step. This is in sharp contrast with the classical Chalk-Harrod mechanism prevalent in platinum chemistry.

Bonding Situation of σ-E-H Complexes in Transition Metal and Main Group Compounds.

The ambiguous bonding situation of σ-E-H (E=Si, B) complexes in transition metal compounds has been rationalized by means of Density Functional Theory calculations. To this end, the combination of the Energy Decomposition Analysis (EDA) method and its Natural Orbital for Chemical Valance (NOCV) extension has been applied to representative complexes described in the literature where the possible η1 versus η2 coordination mode is not unambiguously defined. Our quantitative analyses, which complement previous data based on the application of the Quantum Theory of Atoms in Molecules (QTAIM) approach, indicate that there exists a continuum between genuine η1 and η2 modes depending mainly on the strength of the backdonation. Finally, we also applied this EDA-NOCV approach to related main-group species where the backdonation is minimal.

σ-GeH and Germyl Cationic Pt(II) Complexes.

The low electron count Pt(II) complexes [Pt(NHC')(NHC)][BArF] (where NHC is a N-heterocyclic carbene ligand and NHC' its metalated form) react with tertiary hydrogermanes HGeR3 at room temperature to generate the 14-electron platinum(II) germyl derivatives [Pt(GeR3)(NHC)2][BArF]. Low-temperature NMR studies allowed us to detect and characterize spectroscopically some of the σ-GeH intermediates [Pt(η2-HGeR3)(NHC')(NHC)][BArF] that evolve into the platinum-germyl species. One of these compounds has been characterized by X-ray diffraction studies, and the interaction of the H-Ge bond with the platinum center has been analyzed in detail by computational methods, which suggest that the main contribution is the donation of the H-Ge to a σ*(Pt-C) orbital, but backdonation from the platinum to the σ*(Ge-H) orbital is significant. Primary and secondary hydrogermanes also produce the corresponding platinum-germyl complexes, a result that contrasts with the reactivity observed with primary silanes, in which carbon-silicon bond-forming reactions have been reported. According to density functional theory calculations, the formation of Pt-Ge/C-H bonds is both kinetically and thermodynamically preferred over the competitive reaction pathway leading to Pt-H/C-Ge bonds.

Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources.

The design of new materials with tunable properties and intrinsic recyclability, derived from biomass under mild conditions, stands as a gold standard in polymer chemistry. Reported herein are platinum complexes which catalyze the formation of poly(silylether)s (PSEs) at low catalyst loadings. These polymers are directly obtained from dual-functional biobased building blocks such as 5-hydroxymethylfurfural (HMF) or vanillin, coupled with various dihydrosilanes. Access to different types of copolymer architectures (statistical or alternating) is highlighted by several synthetic strategies. The materials obtained were then characterized as low Tg materials (ranging from -60 to 29 °C), stable upon heating (T-5% up to 301 °C) and resistant towards uncatalyzed methanolysis. Additionally, quantitative chemical recycling of several PSEs could be triggered by acid-catalyzed hydrolysis or methanolysis. These results emphasize the interest of biobased poly(silylether)s as sustainable materials with high recycling potential.

σ-Silane Platinum(II) Complexes as Intermediates in C-Si Bond-Coupling Processes.

Platinum complexes [Pt(NHC')(NHC)][BArF ] (in which NHC' denotes a cyclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH3 to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR')(NHC)][BArF ] through a process that involves the formation of C-Si and Pt-Si bonds with concomitant extrusion of H2 . Low-temperature NMR studies indicate that the process proceeds through initial formation of the σ-SiH complexes [Pt(NHC')(NHC)(HSiH2 R)][BArF ], which are stable at temperatures below -10 °C. At higher temperatures, activation of one Si-H bond followed by a C-Si coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC'-SiH2 R)(NHC)][BArF ], which undergoes a second Si-H bond activation to afford the final products. Computational modeling of the reaction mechanism indicates that the stereochemistry of the silyl/hydride ligands after the first Si-H bond cleavage dictates the nature of the products, favoring the formation of a C-Si bond over a C-H bond, in contrast to previous results obtained for tertiary silanes. Furthermore, the process involves a trans-to-cis isomerization of the NHC ligand before the second Si-H bond cleavage.

Isolation of a Cationic Platinum(II) σ-Silane Complex.

The platinum complex [Pt(It Bui Pr')(It Bui Pr)][BArF ] interacts with tertiary silanes to form stable (<0 °C) mononuclear PtII σ-SiH complexes [Pt(It Bui Pr')(It Bui Pr)(η1 -HSiR3 )][BArF ]. These compounds have been fully characterized, including X-ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual η1 -SiH. However, the energies required for achieving a η2 -SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si-H cleavage leading to the more stable silyl species [Pt(SiR3 )(It Bui Pr)2 ][BArF ] at room temperature.

Cationic Platinum(II) σ-SiH Complexes in Carbon Dioxide Hydrosilation.

The low-electron-count cationic platinum complex [Pt(ItBu')(ItBu)][BArF ], 1, interacts with primary and secondary silanes to form the corresponding σ-SiH complexes. According to DFT calculations, the most stable coordination mode is the uncommon η1 -SiH. The reaction of 1 with Et2 SiH2 leads to the X-ray structurally characterized 14-electron PtII species [Pt(SiEt2 H)(ItBu)2 ][BArF ], 2, which is stabilized by an agostic interaction. Complexes 1, 2, and the hydride [Pt(H)(ItBu)2 ][BArF ], 3, catalyze the hydrosilation of CO2 , leading to the exclusive formation of the corresponding silyl formates at room temperature.

Reactivity of cationic agostic and carbene structures derived from platinum(II) metallacycles.

This paper describes the formation of new platinacyclic complexes derived from the phosphine ligands PiPr2 Xyl, PMeXyl2 , and PMe2 Ar Xyl 2 (Xyl=2,6-Me2 C6 H3 and Ar Xyl 2=2,6-(2,6-Me2 C6 H3 )2 -C6 H3 ) as well as reactivity studies of the trans-[Pt(C^P)2 ] bis-metallacyclic complex 1 a derived from PiPr2 Xyl. Protonation of compound 1 a with [H(OEt2 )2 ][BArF ] (BArF =B[3,5-(CF3 )2 C6 H3 ]4 ) forms a cationic δ-agostic structure 4 a, whereas α-hydride abstraction employing [Ph3 C][PF6 ] produces a cationic platinum carbene trans-[Pt{PiPr2 (2,6-CH(Me)C6 H3 }{PiPr2 (2,6-CH2 (Me)C6 H3 }][PF6 ] (8). Compounds 4 a and 8 react with H2 to yield the same 1:3 equilibrium mixture of 4 a and trans-[PtH(PiPr2 Xyl)2 ][BArF ] (6), in which one of the phosphine ligands participates in a δ-agostic interaction. DFT calculations reveal that H2 activation by 8 occurs at the highly electrophilic alkylidene terminus with no participation of the metal. The two compounds 4 a and 8 experience C-C coupling reactions of a different nature. Thus, 4 a gives rise to complex trans-[PtH{(E)-1,2-bis(2-(PiPr2 )-3-MeC6 H3 )CHCH}] (7) that contains a tridentate diphosphine-alkene ligand, through agostic CH oxidative cleavage and C-C reductive coupling steps, whereas the C-C coupling reaction in 8 involves classical migratory insertion of its [PtCH] and [PtCH2 ] bonds promoted by platinum coordination of CO or CNXyl. The mechanisms of the CC bond-forming reactions have also been investigated by computational methods.

Reactivity of coordinatively unsaturated bis(N-heterocyclic carbene) Pt(II) complexes toward H(2). Crystal structure of a 14-electron Pt(II) hydride complex.

The reactivity toward H2 of coordinatively unsaturated Pt(II) complexes, stabilized by N-heterocyclic carbene (NHC) ligands, is herein analyzed. The cationic platinum complexes [Pt(NHC')(NHC)](+) (where NHC' stands for a cyclometalated NHC ligand) react very fast with H2 at room temperature, leading to hydrogenolysis of the Pt-CH2 bond and concomitant formation of hydride derivatives [PtH(NHC)2](+) or hydrido-dihydrogen complexes [PtH(H2)(NHC)2](+). The latter species release H2 when these compounds are subjected to vacuum. The X-ray structure of complex [PtH(IPr)2][SbF6] revealed its unsaturated nature, exhibiting a true T-shaped structure without stabilization by agostic interactions. Density functional theory calculations indicate that the binding and reaction of H2 in complexes [PtH(H2)(NHC)2](+) is more favored for derivatives bearing aryl-substituted NHCs (IPr, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene and IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) than for those containing tert-butyl groups (I(t)Bu). This outcome is related to the higher close-range steric effects of the I(t)Bu ligands. Accordingly, H/D exchange reactions between hydrides [PtH(NHC)2](+) and D2 take place considerably faster for IPr and IMes* derivatives than for I(t)Bu ones. The reaction mechanisms for both H2 addition and H/D exchange processes depend on the nature of the NHC ligand, operating through oxidative addition transition states in the case of IPr and IMes* or by a σ-complex assisted-metathesis mechanism in the case of I(t)Bu.

Orbital-like motion of hydride ligands around low-coordinate metal centers.

Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital-like motion of hydride ligands around low-coordinate metal centers containing N-heterocyclic carbenes. The hydride movement around the carbene-metal-carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra.

Dehydrocoupling reactions of dimethylamine-borane by Pt(II) complexes: a new mechanism involving deprotonation of boronium cations.

Coordinatively unsaturated Pt(II) complex [Pt(I(t)Bu')(I(t)Bu)](+) stabilized by N-heterocyclic carbene (NHC) ligands dehydrogenates N,N-dimethylamineborane through a mechanism that involves hydride abstraction, assisted by an amine, to yield a platinum-hydride complex [PtH(I(t)Bu')(I(t)Bu)] with concomitant formation of the boronium cation [(NHMe2)2BH2](+). This latter species is very likely in equilibrium with the THF stabilized borenium cation [(NHMe2)(THF)BH2](+), bearing an acidic NH group that is able to protonate the platinum hydride [PtH(I(t)Bu')(I(t)Bu)] releasing H2, the amino borane H2B-NMe2 and regenerating the catalytic [Pt](+) species.

True and masked three-coordinate T-shaped platinum(II) intermediates.

Although four-coordinate square-planar geometries, with a formally 16-electron counting, are absolutely dominant in isolated Pt(II) complexes, three-coordinate, 14-electron Pt(II) complexes are believed to be key intermediates in a number of platinum-mediated organometallic transformations. Although very few authenticated three-coordinate Pt(II) complexes have been characterized, a much larger number of complexes can be described as operationally three-coordinate in a kinetic sense. In these compounds, which we have called masked T-shaped complexes, the fourth position is occupied by a very weak ligand (agostic bond, solvent molecule or counteranion), which can be easily displaced. This review summarizes the structural features of the true and masked T-shaped Pt(II) complexes reported so far and describes synthetic strategies employed for their formation. Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C-H bond-activation processes.

Characterization of a paramagnetic, mononuclear Pt(III)-alkyl complex intermediate in carbon-halogen bond coupling reactions.

Addition of Br(2) or I(2) to 14-electron, cationic Pt(II)-alkyl complexes led to the formation of the corresponding carbon-halogen Pt(II) coupling products. Low temperature experiments with Br(2) allowed us to isolate and characterize crystallographically a very unusual mononuclear, paramagnetic Pt(III)-alkyl intermediate with a seesaw structure that can be further oxidized to a transient Pt(IV) species before reductive carbon-halogen coupling reaction takes place.

Tautomerisation of 2-substituted pyridines to N-heterocyclic carbene ligands induced by the 16†e- unsaturated [Tp(Me2)Ir(III)(C6H5)2] moiety.

The complex [Tp(Me2)Ir(C(6)H(5))(2)(N(2))] reacts with several 2-substituted pyridines to generate N-heterocyclic carbenes resulting from a formal 1,2-hydrogen shift from C(6) to N. In this paper we provide a detailed report of the scope and the mechanistic aspects (both experimental and theoretical) of the tautomerisation of 2-substituted pyridines.

Tuning N-heterocyclic carbenes in T-shaped Pt(II) complexes for intermolecular C-H bond activation of arenes.

Small change matters: T-shaped Pt(II) complexes with less flexible substituents, than, for example, isopropyl or tert-butyl groups, on N-heterocyclic carbene (NHC) ligands allow for C-H bond activation reactions of aromatic compounds (see scheme; BAr(f)(4)(-) =tetrakis[(3,5-trifluoromethyl)phenyl]borate; F yellow, Pt red). NHC substituents that are not highly branched prevent agostic interactions and reduce the barriers to achieve the C-H bond cleavage.

Activation of Si-H and B-H bonds by Lewis acidic transition metals and p-block elements: same, but different.

In this Perspective we discuss the ability of transition metal complexes to activate and cleave the Si-H and B-H bonds of hydrosilanes and hydroboranes (tri- and tetra-coordinated) in an electrophilic manner, avoiding the need for the metal centre to undergo two-electron processes (oxidative addition/reductive elimination). A formal polarization of E-H bonds (E = Si, B) upon their coordination to the metal centre to form σ-EH complexes (with coordination modes η1 or η2) favors this type of bond activation that can lead to reactivities involving the formation of transient silylium and borenium/boronium cations similar to those proposed in silylation and borylation processes catalysed by boron and aluminium Lewis acids. We compare the reactivity of transition metal complexes and boron/aluminium Lewis acids through a series of catalytic reactions in which pieces of evidence suggest mechanisms involving electrophilic reaction pathways.

C-H bond activation reactions of ethers that generate iridium carbenes.

Two important objectives in organometallic chemistry are to understand C-H bond activation reactions mediated by transition metal compounds and then to develop efficient ways of functionalizing the resulting products. A particularly ambitious goal is the generation of metal carbenes from simple organic molecules; the synthetic chemist can then take advantage of the almost unlimited reactivity of this metal-organic functionality. This goal remains very difficult indeed with saturated hydrocarbons, but it is considerably more facile for molecules that possess a heteroatom (such as ethers), because coordination of the heteroatom to the metal renders the ensuing C-H activation an intramolecular reaction. In this Account, we focus on the activation reaction of different types of unstrained ethers, both aliphatic and hemiaromatic, by (mostly) iridium compounds. We emphasize our recent results with the Tp(Me2)Ir(C(6)H(5))(2)(N(2)) (1.N(2)) complex (where Tp(Me2) denotes hydrotris(3,5-dimethylpyrazolyl)borate). Most of the reactivity observed with this system, and with related electronically unsaturated iridium species, starts with a C-H activation reaction, which is then followed by reversible alpha-hydrogen elimination. An alpha-C-H bond is, in every instance, broken first; when there is a choice, cleavage of the stronger terminal C(sp(3))-H bonds is always preferred over the weaker internal C(sp(3))-H (methylene) bonds of the ether. Nevertheless, competitive reactions of the unsaturated [Tp(Me2)Ir(C(6)H(5))(2)] iridium intermediate with ethers that contain C(sp(3))-H and C(sp(2))-H bonds are also discussed. We present theoretical evidence for a sigma-complex-assisted metathesis mechanism (sigma-CAM), although for other systems oxidative addition and reductive elimination events can be effective reaction pathways. We also show that additional unusual chemical transformations may occur, depending on the nature of the ether, and can result in C-O and C-C bond-breaking and bond-forming reactions, leading to the formation of more elaborate molecules. Although the possibility of extending these results to saturated hydrocarbons appears to be limited for this iridium system, the findings described in this Account are of fundamental importance for various facets of C-H bond activation chemistry, and with suitable modifications of the ancillary ligands, they could be even broader in scope. We further discuss experimental and theoretical studies on unusual alkene-to-alkylidene equilibria for some of the products obtained in the reactions of iridium complex 1.N(2) with alkyl aryl ethers. The rearrangement involves reversible alpha- and beta-hydrogen eliminations, with a rate-determining metal inversion step (supported by theoretical calculations); the alkylidene is always favored thermodynamically over the alkene. This startling result contrasts with the energetically unfavorable isomerization of free ethene to ethylidene (by about 80 kcal mol(-1)), showing that the tautomerism equilibrium can be directed toward one product or the other by a judicious choice of the transition metal complex.

Enhancing the catalytic properties of well-defined electrophilic platinum complexes.

Platinum complexes have been often considered as the least reactive of the group 10 triad metals. Slow kinetics are behind this lack of reactivity but, still, some industrially relevant catalytic process are dominated by platinum compounds and sometimes different selectivities can be found in comparison to Ni or Pd. Nevertheless, during the last years, it has been reported that the catalytic behaviour of well-defined platinum derivatives can be improved through a judicious choice of their electronic and steric properties, leading to highly electrophilic or low-electron count platinum systems. In this feature article, we highlight some catalytic processes in which well-defined electrophilic platinum complexes or coordinatively unsaturated systems play an important role in their catalytic activity.

Reversible carbon-boron bond formation at platinum centers through σ-BH complexes.

A reversible carbon-boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I t BuiPr')(I t BuiPr)][BArF], 1, with tricoordinated boranes HBR2. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR2)(I t BuiPr')(I t BuiPr)][BArF], one of which has been isolated. From -15 to +10 °C, the σ-BH species undergo a carbon-boron coupling process leading to the platinum hydride derivative [Pt(H)(I t BuiPr-BR2)(I t BuiPr)][BArF], 4. Surprisingly, these compounds are thermally unstable undergoing carbon-boron bond cleavage at room temperature that results in the 14-electron Pt(ii) boryl species [Pt(BR2)(I t BuiPr)2][BArF], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon-boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C-H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon-boron coupling reactions at transition metal centers.

Platinum nanoparticles stabilized by N-heterocyclic thiones. Synthesis and catalytic activity in mono- and di-hydroboration of alkynes.

N-Heterocyclic Thiones (NHT) proved to be efficient ligands for the stabilization of small platinum nanoparticles (1.3-1.7 nm), synthesized by decomposition of [Pt(dba)2], under a H2 atmosphere, in the presence of variable sub-stoichiometric amounts of the NHT. Full characterization by means of TEM, HR-TEM, NMR, ICP, TGA and XPS have been carried out, providing information about the nature of the metal nanoparticles and the interaction of the NHT ligands to the metal surface. Importantly, DFT calculations indicate that some NHT ligands interact with the metal through the C[double bond, length as m-dash]C double bond of the imidazole fragment in addition to the sulfur atom, thus providing additional stabilization to the nanoparticles. According to XPS, TGA and ICP techniques, the surface coverage by the ligand increases by decreasing the size of the substituents on the nitrogen atom. The platinum nanoparticles have been used as catalyst in the hydroboration of alkynes. The most active system is that with a less covered surface area lacking an interaction of the ligand by means of the C[double bond, length as m-dash]C double bond. This catalyst hydroborates alkynes with excellent selectivities towards the monoborylated anti-Markovnikov product (vinyl-boronate) when one equiv. of borane is used. Very interestingly, aliphatic alkynes undergo a second hydroborylation process leading to the corresponding 1,1- and 1,2-diboroylated species with good selectivities towards the former.