Molecular Dihydrogen Activation by (C5Me5)M/N (M=Rh, Ir) Transition Metal Frustrated Lewis Pairs: Reversible Proton Migration to, and Proton Abstraction from, the C5Me5 Ligand.

The masked transition-metal frustrated Lewis pairs [Cp*M(κ3N,N',N''-L)][SbF6] (Cp*=η5-C5Me5; M=Ir, 1, Rh, 2; HL=pyridinyl-amidine ligand) reversibly activate H2 under mild conditions rendering the hydrido derivatives [Cp*MH(κ2N,N'-HL)][SbF6] observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula [(Cp*H)Rh(κ2N,N'-HL)][SbF6] (5 a-d) is obtained by reductive elimination of Cp*H from 4. The formation of 5 a-d was elucidated by means of DFT calculations. Finally, when 2 reacts with D2, the Cp* and Cp*H ligands of the resulting rhodium complexes 4 and 5, respectively, are deuterated as a result of a reversible hydrogen abstraction from the Cp* ligand and D2 activation at rhodium.

Dynamic Configuration on a Chiral-at-Rhodium Catalyst Featuring a Flexible Tetradentate Ligand.

The unique dynamic configuration of an enantioselective chiral-at-metal catalyst based on Rh(III) and a non-chiral tetradentate ligand is described and resolved. At room temperature, the catalyst undergoes a dynamic configuration process leading to the formation of two interconvertible metal-stereoisomers, remarkably without racemization. Density functional theory (DFT) calculations indicate that this metal-isomerization proceeds via a concerted transition state, which features a trigonal bipyramidal geometry stabilized by the tetradentate ligand. Furthermore, the resolved enantiopure complex shows high catalytic enantioinduction in the Friedel-Crafts reaction, achieving enantiomeric ratios as high as 99 : 1.

Activation of H-H, HO-H, C(sp2)-H, C(sp3)-H, and RO-H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M/N (M = Rh, Ir) Couples.

Reaction of the dimers [(Cp*MCl)2(µ-Cl)2] (Cp* = η5-C5Me5) with Ph2PCH2CH2NC(NH(p-Tolyl))2 (H2L) in the presence of NaSbF6 affords the chlorido complexes [Cp*MCl(κ2N,P-H2L)][SbF6] (M = Rh, 1; Ir, 2). Upon treatment with aqueous NaOH, solutions of 1 and 2 yield the corresponding complexes [Cp*M(κ3N,N',P-HL)][SbF6] (M = Rh, 3; Ir, 4) in which the ligand HL presents a fac κ3N,N',P coordination mode. Treatment of THF solutions of complexes 3 and 4 with hydrogen gas, at room temperature, results in the formation of the metal hydrido-complexes [Cp*MH(κ2N,P-H2L)][SbF6] (M = Rh, 5; Ir, 6) in which the N(p-Tolyl) group has been protonated. Complexes 3 and 4 react with deuterated water in a reversible fashion resulting in the gradual deuteration of the Cp* group. Heating at 383 K THF/H2O solutions of the complexes 3 and 4 affords the orthometalated complexes [Cp*M(κ3C,N,P-H2L-H)][SbF6] [M = Rh, 7; Ir, 8, H2L-H = Ph2PCH2CH2NC(NH(p-Tolyl))(NH(4-C6H3Me))], respectively. At 333 K, complexes 3 and 4 react in THF with methanol, primary alcohols, or 2-propanol giving the metal-hydrido complexes 5 and 6, respectively. The reaction involves the acceptorless dehydrogenation of the alcohols at a relatively low temperature, without the assistance of an external base. The new complexes have been characterized by the usual analytical and spectroscopic methods including the X-ray diffraction determination of the crystal structures of complexes 1-5, 7, and 8. Notably, the chlorido complexes 1 and 2 crystallize both as enantiopure conglomerates and as racemates. Reaction mechanisms are proposed based on stoichiometric reactions, nuclear magnetic resonance studies, and X-ray crystallography as well as density functional theory calculations.

Preparation of Mixed Bis-N-Heterocyclic Carbene Rhodium(I) Complexes.

A series of mixed bis-NHC rhodium(I) complexes of type RhCl(η2-olefin)(NHC)(NHC') have been synthesized by a stepwise reaction of [Rh(µ-Cl)(η2-olefin)2]2 with two different NHCs (NHC = N-heterocyclic carbene), in which the steric hindrance of both NHC ligands and the η2-olefin is critical. Similarly, new mixed coumarin-functionalized bis-NHC rhodium complexes have been prepared by a reaction of mono NHC complexes of type RhCl(NHC-coumarin)(η2,η2-cod) with the corresponding azolium salt in the presence of an external base. Both synthetic procedures proceed selectively and allow the preparation of mixed bis-NHC rhodium complexes in good yields.

Selective Oxidation of Glycerol via Acceptorless Dehydrogenation Driven by Ir(I)-NHC Catalysts.

Iridium(I) compounds featuring bridge-functionalized bis-NHC ligands (NHC = N-heterocyclic carbene), [Ir(cod)(bis-NHC)] and [Ir(CO)2(bis-NHC)], have been prepared from the appropriate carboxylate- or hydroxy-functionalized bis-imidazolium salts. The related complexes [Ir(cod)(NHC)2]+ and [IrCl(cod)(NHC)(cod)] have been synthesized from a 3-hydroxypropyl functionalized imidazolium salt. These complexes have been shown to be robust catalysts in the oxidative dehydrogenation of glycerol to lactate (LA) with dihydrogen release. High activity and selectivity to LA were achieved in an open system under low catalyst loadings using KOH as a base. The hydroxy-functionalized bis-NHC catalysts are much more active than both the carboxylate-functionalized ones and the unbridged bis-NHC iridium(I) catalyst with hydroxyalkyl-functionalized NHC ligands. In general, carbonyl complexes are more active than the related 1,5-cyclooctadiene ones. The catalyst [Ir(CO)2{(MeImCH2)2CHOH}]Br exhibits the highest productivity affording TONs to LA up to 15,000 at very low catalyst loadings.

Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes.

The dinuclear complex [Rh(µ-Cl)(η2 -coe)(IPr)]2 is an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations support a hydride-free pathway entailing intramolecular oxidative protonation of a π-alkyne by a κ1 N-hydroxypyridine ligand. Subsequent O-nucleophilic attack on a metallacyclopropene species affords an O-alkenyl-2-oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate-determining step.

Preparation of Butadienylpyridines by Iridium-NHC-Catalyzed Alkyne Hydroalkenylation and Quinolizine Rearrangement.

Iridium(I) N-heterocyclic carbene complexes of formula Ir(κ2 O,O'-BHetA)(IPr)(η2 -coe) [BHetA=bis-heteroatomic acidato, acetylacetonate or acetate; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-carbene; coe=cyclooctene] have been prepared by treating Ir(κ2 O,O'-BHetA)(η2 -coe)2 complexes with IPr. These complexes react with 2-vinylpyridine to afford the hydrido-iridium(III)-alkenyl cyclometalated derivatives IrH(κ2 O,O'-BHetA)(κ2 N,C-C7 H6 N)(IPr) through the iridium(I) intermediate Ir(κ2 O,O'-BHetA)(IPr)(η2 -C7 H7 N). The cyclometalated IrH(κ2 O,O'-acac)(κ2 N,C-C7 H6 N)(IPr) complex efficiently catalyzes the hydroalkenylation of aromatic and aliphatic terminal alkynes and enynes with 2-vinylpyridine to afford 2-(4R-butadienyl)pyridines with Z,E configuration as the major reaction products (yield up to 89 %). In addition, unprecedented (Z)-2-butadienyl-5R-pyridine derivatives have been obtained as minor reaction products (yield up to 21 %) from the elusive 1Z,3gem-butadienyl hydroalkenylation products. These compounds undergo a thermal 6π-electrocyclization to afford bicyclic 4H-quinolizine derivatives that, under catalytic reaction conditions, tautomerize to 6H-quinolizine to afford the (Z)-2-(butadienyl)-5R-pyridine by a retro-electrocyclization reaction.

Impact of Green Cosolvents on the Catalytic Dehydrogenation of Formic Acid: The Case of Iridium Catalysts Bearing NHC-phosphane Ligands.

The catalysts [Ir(COD)(κ3-P,C,P'-PCNHCP)]BF4 and [Ir(COD)(κ2-P,C-PCNHCO)]BF4 proved to be active in the solventless dehydrogenation of formic acid. The impact of various cosolvents on the activity was evaluated, showing an outstanding improvement of the catalytic performance of [Ir(COD)(κ2-P,C-PCNHCO)]BF4] in "green" organic carbonates: namely, dimethyl carbonate (DMC) and propylene carbonate (PC). The TOF1h value for [Ir(COD)(κ2-P,C-PCNHCO)]BF4 increases from 61 to 988 h-1 upon changing from solventless conditions to a 1/1 (v/v) DMC/HCOOH mixture. However, in the case of [Ir(COD)(PCNHCP)]BF4, only a marginal improvement from 156 to 172 h-1 was observed under analogous conditions. Stoichiometric experiments allowed the identification of various key reaction intermediates, providing valuable information on their reactivity. Experimental data and DFT calculations point to the formation of dinuclear species as the catalyst deactivation pathway, which is prevented in the presence of DMC and PC.

Rhodium(I)-NHC Complexes Bearing Bidentate Bis-Heteroatomic Acidato Ligands as gem-Selective Catalysts for Alkyne Dimerization.

A series of Rh(κ2 -BHetA)(η2 -coe)(IPr) complexes bearing 1,3-bis-hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reaction of the dinuclear precursor [Rh(µ-Cl)(IPr)(η2 -coe)]2 with the corresponding anionic BHetA species. The RhI -NHC-BHetA compounds catalyze the dimerization of aryl alkynes, showing excellent selectivity for the head-to-tail enynes. Among them, the acetanilidato-based catalyst has shown an outstanding catalytic performance reaching unprecedented TOF levels of 2500 h-1 with complete selectivity for the gem-isomer. Investigation of the reaction mechanism supports a non-oxidative pathway in which the BHetA ligand behaves as proton shuttle through intermediate κ1 -HBHetA species. However, in the presence of pyridine as additive, the identification of the common RhIII H(C≡CPh)2 (IPr)(py)2 intermediate gives support for an alternative oxidative route.

Ligand Lability Driven by Metal-to-Borane Pseudorotation: A Mechanism for Ligand Exchange.

The discovery of systems that interact with small molecules plays a vital facilitating role in the development of devices that show sensitivity to their surroundings and an ability to quickly relay chemical and physical information. Herein, we report on the reaction of [NiCl2(dppe)] with decaborane that produces in usable yield a new 11-vertex nickelaborane, [7,7-(dppe)-nido-7-NiB10H12] (1), which shows interesting reactivity and functionality toward carbon monoxide and ethylisonitrile. This contribution describes the synthesis and full structural characterization of 1 and its small-molecule EtNC and CO adducts, 2 and 3, and delineates the dynamic molecular behavior of all of these species in solution. This information sets a foundation from which more advanced work on this and related metallaborane systems can be conceived and provides a more general reference to how NMR spectroscopy, combined with DFT calculations, can be used to analyze the precise locomotion of labile ligands around a metal center held within a borane cluster.

Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair.

[Cp*Rh(κ3 N,N',P-L)][SbF6 ] (Cp*=C5 Me5 ), bearing a guanidine-derived phosphano ligand L, behaves as a "dormant" frustrated Lewis pair and activates H2 and H2 O in a reversible manner. When D2 O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp3 )-H bond activation.

Metal as Source of Chirality in Octahedral Complexes with Tripodal Tetradentate Ligands.

The challenging control of the absolute configuration of chiral-at-metal complexes is efficiently achieved using the tripodal tetradentate ligand L. The optical resolution of rac-[RhCl2(κ4C,N,N',P-L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κ4C,N,N',P-L)A(Solv)][SbF6]n that enantioselectively catalyze the Diels-Alder reaction between methacrolein and HCp with enantiomeric ratio of up to >99/1. The nature of the active species, the origin of the enantioselectivity and mechanistic details are disclosed by means of NMR spectroscopy and DFT studies.

Zwitterionic Rhodium and Iridium Complexes Based on a Carboxylate Bridge-Functionalized Bis-N-heterocyclic Carbene Ligand: Synthesis, Structure, Dynamic Behavior, and Reactivity.

A series of water-soluble zwitterionic complexes featuring a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand of formula [Cp*MIIICl{(MeIm)2CHCOO}] and [MI(diene){(MeIm)2CHCOO}] (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; M = Rh, Ir; MeIm = 3-methylimidazol-2-yliden-1-yl; diene = 1,5-cyclooctadiene (cod), norbornadiene (nbd)) were prepared from the salt [(MeImH)2CHCOO]Br and suitable metal precursor. The solid-state structure of both types of complexes shows a boat-shaped six-membered metallacycle derived of the κ2C,C' coordination mode of the bis-NHC ligand. The uncoordinated carboxylate fragment is found at the bowsprit position in the Cp*MIII complexes, whereas in the MI(diene) complexes it is at the flagpole position of the metallacycle. The complexes [RhI(diene){(MeIm)2CHCOO}] (diene = cod, nbd) exist as two conformational isomers in dichloromethane, bowsprit and flagpole, that interconvert through the boat-to-boat inversion of the metallacycle. An inversion barrier of ∼17 kcal·mol-1 was determined by two-dimensional exchange spectroscopy NMR measurements for [RhI(cod){(MeIm)2CHCOO}]. Reaction of zwitterionic Cp*MIII complexes with methyl triflate or tetrafluoroboric acid affords the cationic complexes [Cp*MIIICl{(MeIm)2CHCOOMe}]+ or [Cp*MIIICl{(MeIm)2CHCOOH}]+ (M = Rh, Ir) featuring carboxy and methoxycarbonyl functionalized methylene-bridged bis-NHC ligands, respectively. Similarly, complexes [MI(diene){(MeIm)2CHCOOMe}]+ (M = Rh, Ir) were prepared by alkylation of the corresponding zwitterionic MI(diene) complexes with methyl triflate. In contrast, reaction of [IrI(cod){(MeIm)2CHCOO}] with HBF4·Et2O (Et = ethyl), CH3OTf, CH3I, or I2 gives cationic iridium(III) octahedral complexes [IrIIIX(cod){(MeIm)2CHCOO}]+ (X = H, Me, or I) featuring a tripodal coordination mode of the carboxylate bridge-functionalized bis-NHC ligand. The switch from κ2C,C' to κ3C,C',O coordination of the bis-NHC ligand accompanying the oxidative addition prevents the coordination of the anions eventually formed in the process that remain as counterions.

The Stepwise Reaction of Rhodium and Iridium Complexes of Formula [MCl2 (κ4 C,N,N',P-L)] with Silver Cations: A Case of trans-Influence and Chiral Self-Recognition.

Acetonitrile suspensions of the dichlorido complexes [MCl2 (κ4 C,N,N',P-L)] [M=Rh (1), Ir (2)] react with AgSbF6 in a 1:2 molar ratio affording the bis-acetonitrile complexes [M(κ4 C,N,N',P-L)(NCMe)2 ][SbF6 ]2 (3 and 4). The reaction takes place in a sequential manner and the intermediates can be isolated varying the M:Ag molar ratio. In a 2:1 molar ratio, it affords the dimetallic monochlorido-bridged compounds [{MCl(κ4 C,N,N',P-L)}2 (µ-Cl)][SbF6 ] (5 and 6). In a 1:1 molar ratio, the monosubstituted solvato-complexes [MCl(κ4 C,N,N',P-L)(Solv)][SbF6 ] (Solv=H2 O, MeCN, 7-10) were obtained. Finally, in a 2:3 molar ratio, it gives complexes 11 and 12 of formula [{M(κ4 C,N,N',P-L)(NCMe)(µ-Cl)}2 Ag][SbF6 ]3 in which a silver cation joints two cationic monosubstituted acetonitrile-complexes [MCl(κ4 C,N,N',P-L)(NCMe)]+ through the remaining chlorido ligands and two Ag⋅⋅⋅C interactions with one of the phenyl rings of each PPh2 group. In all the complexes, the aminic nitrogen and the central metal atom are stereogenic centers. In the trimetallic complexes 11 and 12, the silver atom is also a stereogenic center. The formation of the cation of the dimetallic complexes 5 and 6, as well as that of the trimetallic complexes 11 and 12, takes place with chiral molecular self-recognition. Experimental data and DFT calculations provide plausible explanations for the observed molecular recognition. The new complexes have been characterized by analytical, spectroscopic means and by X-ray diffraction methods.

Temperature Dual Enantioselective Control in a Rhodium-Catalyzed Michael-Type Friedel-Crafts Reaction: A Mechanistic Explanation.

By changing the temperature from 283 to 233 K, the S (99 % ee) or R (96 % ee) enantiomer of the Friedel-Crafts (FC) adduct of the reaction between N-methyl-2-methylindole and trans-ß-nitrostyrene can be obtained by using (SRh ,RC )-[(η(5) -C5 Me5 )Rh{(R)-Prophos}(H2 O)][SbF6 ]2 as the catalyst precursor. This catalytic system presents two other uncommon features: 1) The ee changes with reaction time showing trends that depend on the reaction temperature and 2) an increase in the catalyst loading results in a decrease in the ee of the S enantiomer. Detection and characterization of the intermediate metal-nitroalkene and metal-aci-nitro complexes, the free aci-nitro compound, and the FC adduct-complex, together with solution NMR measurements, theoretical calculations, and kinetic studies have allowed us to propose two plausible alternative catalytic cycles. On the basis of these cycles, all the above-mentioned observations can be rationalized. In particular, the reversibility of one of the cycles together with the kinetic resolution of the intermediate aci-nitro complexes account for the high ee values achieved in both antipodes. On the other hand, the results of kinetic measurements explain the unusual effect of the increment in catalyst loading.

Intramolecular C-H oxidative addition to iridium(I) in complexes containing a N,N'-diphosphanosilanediamine ligand.

The iridium(I) complexes of formula Ir(cod)(SiNP)(+) (1(+)) and IrCl(cod)(SiNP) (2) are easily obtained from the reaction of SiMe2{N(4-C6H4CH3)PPh2}2 (SiNP) with [Ir(cod)(CH3CN)2](+) or [IrCl(cod)]2, respectively. The carbonylation of [1][PF6] affords the cationic pentacoordinated complex [Ir(CO)(cod)(SiNP)](+) (3(+)), while the treatment 2 with CO gives the cation 3(+) as an intermediate, finally affording an equilibrium mixture of IrCl(CO)(SiNP) (4) and the hydride derivative of formula IrHCl(CO)(SiNP-H) (5) resulting from the intramolecular oxidative addition of the C-H bond of the SiCH3 moiety to the iridium(I) center. Furthermore, the prolonged exposure of [3]Cl or 2 to CO resulted in the formation of the iridium(I) pentacoordinated complex Ir(SiNP-H)(CO)2 (6). The unprecedented κ(3)C,P,P' coordination mode of the [SiNP-H] ligand observed in 5 and 6 has been fully characterized in solution by NMR spectroscopy. In addition, the single-crystal X-ray structure of 6 is reported.

Reactivity of Ir(I)-aminophosphane platforms towards oxidants.

The iridium(I)-aminophosphane complex [Ir{κ3C,P,P'-(SiNP-H)}(cod)] has been prepared by reaction of [IrCl(cod)(SiNP)] with KCH3COO. DFT calculations show that this reaction takes place through an unexpected outer sphere mechanism (SiNP = SiMe2{N(4-C6H4Me)PPh2}2; SiNP-H = CH2SiMe{N(4-C6H4Me)PPh2}2). The reaction of [IrCl(cod)(SiNP)] or [Ir{κ3C,P,P'-(SiNP-H)}(cod)] with diverse oxidants has been explored, yielding a range of iridium(III) derivatives. On one hand, [IrCl(cod)(SiNP)] reacts with allyl chloride rendering the octahedral iridium(III) derivative [IrCl2(η3-C3H5)(SiNP)], which, in turn, reacts with tert-butyl isocyanide yielding the substitution product [IrCl(η3-C3H5)(CNtBu)(SiNP)]Cl via the observed intermediate [IrCl2(η1-C3H5)(CNtBu)(SiNP)]. On the other hand, the reaction of [Ir{κ3C,P,P'-(SiNP-H)}(cod)] with [FeCp2]X (X = PF6, CF3SO3), I2 or CF3SO3CH3 results in the metal-centered two-electron oxidation rendering a varied assortment of iridium(III) compounds. [Ir{κ3C,P,P'-(SiNP-H)}(cod)] reacts with [FeCp2]+ (1 : 2) in acetonitrile affording [Ir{κ3C,P,P'-(SiNP-H)}(CH3CN)3]2+ isolated as both the triflato and the hexafluorophosphato derivatives. Also, the reaction of [Ir{κ3C,P,P'-(SiNP-H)}(cod)] with I2 (1 : 1) yields a mixture of iridium(III) derivatives, namely the mononuclear compound [IrI(κ2P,P'-SiNP)(η2,η3-C8H11)]I, containing the η2,η3-cycloocta-2,6-dien-1-yl ligand, and two isomers of the dinuclear derivative [Ir2{κ3C,P,P'-(SiNP-H)}2(µ-I)3]I, the first species being isolated in low yield. DFT calculations indicate that [IrI(κ2P,P'-SiNP)(η2,η3-C8H11)]I forms as the result of a bielectronic oxidation of iridium(I) followed by the deprotonation of the cod ligand by iodide and the protonation of the methylene moiety of the [Ir{κ3C,P,P'-(SiNP-H)}] platform by the newly formed HI. Finally, the oxidation of [Ir{κ3C,P,P'-(SiNP-H)}(cod)] by methyl triflate proceeds via a hydride abstraction from the cod ligand, with the elimination of methane and the formation of the η2,η3-cycloocta-2,6-dien-1-yl ligand with the concomitant two-electron oxidation of the iridium centre. The crystal structures of selected compounds have been determined.

ß-(Z)-Selective alkyne hydrosilylation by a N,O-functionalized NHC-based rhodium(I) catalyst.

Neutral and cationic cyclooctadiene rhodium(I) complexes with a lutidine-derived polydentate ligand having NHC and methoxy side-donor functions, [RhBr(cod)(κC-tBuImCH2PyCH2OMe)] and [Rh(cod)(κ2C,N-tBuImCH2PyCH2OMe)]PF6, have been prepared. Carbonylation of the cationic compound yields the dicarbonyl complex [Rh(CO)2(κ2C,N-tBuImCH2PyCH2OMe)]PF6 whereas carbonylation of the neutral compound affords a mixture of di- and monocarbonyl neutral complexes [RhBr(CO)2(κC-tBuImCH2PyCH2OMe)] and [RhBr(CO)(κ2C,N-tBuImCH2PyCH2OMe)]. These complexes efficiently catalyze the hydrosilylation of 1-hexyne with HSiMe2Ph with a marked selectivity towards the ß-(Z)-vinylsilane product. Catalyst [RhBr(CO)(κ2C,N-tBuImCH2PyCH2OMe)] showed a superior catalytic performance, in terms of both activity and selectivity, and has been applied to the hydrosilylation of a range of 1-alkynes and phenylacetylene derivatives with diverse hydrosilanes, including HSiMe2Ph, HSiMePh2, HSiPh3 and HSiEt3, showing excellent ß-(Z) selectivity for the hydrosilylation of linear aliphatic 1-alkynes. Hydrosilylation of internal alkynes, such as diphenylacetylene and 1-phenyl-1-propyne, selectively affords the syn-addition vinylsilane products. The ß-(Z) selectivity of these catalysts contrasts with that of related rhodium(I) catalysts based on 2-picolyl-functionalised NHC ligands, which were reported to be ß-(E) selective. An energy barrier ΔG‡ of 19.8 ± 2.0 kcal mol-1 (298 K) has been determined from kinetic studies on the hydrosilylation of 1-hexyne with HSiMe2Ph. DFT studies suggest that the methoxy-methyl group is unlikely to be involved in the activation of hydrosilane, and then hydrosilane activation is likely to proceed via a classical Si-H oxidative addition.

Cobalt-catalysed nucleophilic fluorination in organic carbonates.

The novel P-N ligand 1-((diphenylphosphaneyl)methyl)-1H-benzo-1,2,3-triazole (1), based on a benzotriazole scaffold, has been prepared. The reaction of 1 with [CoCp*(CH3CN)3][BF4]2 and [CoCp*(I)2]2 (Cp* = pentamethylcyclopentadienyl) affords the chelate complexes [CoCp*(CH3CN)(P-N)][BF4]2 (2) and [CoCp*(I)(P-N)]I (3), respectively. Complexes 2 and 3 were studied as catalysts in the fluorination of aromatic and aliphatic acyl chlorides in CH2Cl2, with 3 showing notably higher activities than 2. Subsequently, organic carbonates (dimethyl carbonate and propylene carbonate) were also employed as solvents, which led to shorter reaction times and to the broadening of the substrate scope to a variety of aliphatic halides. Comparative studies between 3 and the analogous complex [CoCp*(I)2(PMePh2)], which features a monodentate phosphane ligand, showed that higher yields were obtained in the case of the former. DFT calculations and experimental studies were performed in order to shed light on the reaction mechanism, which entails the formation of a cobalt fluoride species that reacts via nucleophilic attack with the substrate to afford the corresponding fluorinated compounds.

Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand.

The iridium(III) hydride compound [IrH{κ3C,P,P'-(SiNP-H)}(CNtBu)2][PF6] (1PF6) was obtained by reaction of [Ir(SiNP)(cod)][PF6] with CNtBu as the result of the intramolecular oxidative addition of the SiCH2-H bond to iridium(I) [SiNP = Si(CH3)2{N(4-tolyl)PPh2}2, SiNP-H = CH2Si(CH3){N(4-tolyl)PPh2}2]. The mechanism of the reaction was investigated by NMR spectroscopy and DFT calculations showing that the pentacoordinated intermediate [Ir(SiNP)(cod)(CNtBu)][PF6] (2PF6) forms in the first place and that further reacts with CNtBu, affording the square planar intermediate [Ir(SiNP)(CNtBu)2][PF6] (3PF6) that finally undergoes the intramolecular oxidative addition of the SiCH2-H bond. The reactivity of 1PF6 was investigated. On one hand, the reaction of 1PF6 with N-chlorosuccinimide or N-bromosuccinimide provides the haloderivatives [IrX{κ3C,P,P'-(SiNP-H)}(CNtBu)2][PF6] (X = Cl, 4PF6; Br, 5PF6), and the reaction of 5PF6 with AgPF6 in the presence of acetonitrile affords the solvato species [Ir{κ3C,P,P'-(SiNP-H)}(CH3CN)(CNtBu)2]2+ (62+) isolated as the hexafluorophosphate salt. On the other hand, the reaction of 1PF6 with HBF4 gives the iridium(III) compound [IrH(CH2SiF2CH3)(HNP)2(CNtBu)2][BF4] (7BF4) as the result of the formal addition of hydrogen fluoride to the Si-N bonds of 1+ [HNP = HN(4-tolyl)PPh2]. A similar outcome was observed in the reaction of 1PF6 with CF3COOH rendering 7PO2F2. In this case the intermediate [IrH{κ2C,P-CH2SiMeFN(4-tolyl)PPh2}(HNP)(CNtBu)2]+ (8+) was observed and characterised in situ by NMR spectroscopy. DFT calculations suggests that the reaction goes through the sequential protonation of the nitrogen atom of the Si-N-P moiety followed by the formal addition of fluoride ion to silicon. Also, the crystal structures of SiNP, 1PF6, 4PF6 and 7BF4 have been determined by X-ray diffraction measurements.