Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex

A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2'-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.     

Co3O4纳米晶催化氧化甲烷的理论研究：C-H键活化的晶面效应及活性中心

甲烷是一种在自然界中大量存在的原材料,在取代原油和合成重要化工产品等许多领域具有潜在的应用价值. 然而,由于CH₄中C-H键的键能特别大（约~4.5 eV）,如何实现甲烷的绿色有效转化在化学化工领域仍然是一个挑战. 本文采用密度泛函理论对Co₃O₄（001）和（011）晶面活化甲烷C-H键的机理进行了理论研究,得到了如下结论：（1） CH₄的C-H键在Co₃O₄晶面的解离具有很高的活性,只需要克服大约1 eV的能垒;（2）与Co^2＋相连的Co-O离子对是CH₄活化的活性位点,其中两个带正负电荷的离子对C-H解离起着协同作用,帮助产生Co-CH₃和O-H物种;（3）（011）面的反应活性明显大于（001）面,与实验的观察一致. 本文的计算结果表明,Co₃O₄纳米晶面对CH₄中C-H键的活化表现出明显的晶面效应和结构敏感效应,Co-O离子对活性中心对于活化惰性的C-H键发挥了关键作用.     

Facile allylic C-H bond activation on the bridging disulfide ligand in the Ru(III) dinuclear complex having a conjugated RuSSRu core

Treatment of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1), which is prepared by the reaction of [[RuCl(P(OCH(3))(3))(2)](2)(mu-S(2))(mu-Cl)(2)] (2) with 4 equiv of AgCF(3)SO(3), with terminal alkenes such as 1-pentene, allyl ethyl ether, allyl phenyl ether, 1,4-hexadiene, and 3-methyl-1-butene, resulted in the formation of complexes carrying a C(3)S(2) five-membered ring, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CR(1)R(2)S]](CF(3)SO(3))(4) (3, R(1) = CH(2)CH(3), R(2) = H, 40%; 4, R(1) = OCH(2)CH(3), R(2) = H, 60%; 5, R(1) = OC(6)H(5), R(2) = H, 73%; 6, R(1) = CH=CHCH(3), R(2) = H, 48%; 7, R(1) = R(2) = CH(3), 40%). Reaction of 1 with methylenecycloalkanes was found to give several different types of products, depending on the ring size of the substrates. A trace of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(CH(2)CH(2))CH(CH(3))S]](CF(3)SO(3))(4) (9) having a C(2)S(2) four-membered ring to bridge the two Ru atoms was obtained by the reaction of 1 with methylenecyclobutane, whereas the reaction with methylenecyclohexane gave [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-S(CH(2)(C=CHCH(2)CH(2)CH(2)CH(2))S)](CF(3)SO(3))(3) (10) in 69% yield via C-S bond formation and elimination of a proton. Throughout these reactions with alkenes giving a variety of products, the activation of the allylic C-H bond is always the essential and initial key step.     

Palladium(0) nanoparticle-catalyzed sp C-H activation: a convenient route to alkyl-aryl ketones by direct acylation of aryl bromides and iodides with aldehydes

Palladium(0) nanoparticles efficiently catalyze aliphatic aldehyde C-H functionalization by aryl halides to produce alkyl-aryl ketones in good yields. A wide range of substituted aryl and hetero-aryl bromides/iodides and open-chain aldehydes of varied chain length participated in this reaction.     

Methylene transfer from SnMe groups mediated by a rhodium(I) pincer complex: Sn-C, C-C, and C-H bond activation

The PCP-Rh(I) complex 1a based on the [1,3-phenylenebis(methylene)]bis(diisopropylphosphine) ligand reacts with [diazo(phenyl)methyl]trimethylstannane (2) at room temperature to give novel pincer-type phenyl(dimethylstannyl)methylene]hydrazinato complex 3a. The reaction sequence involves a unique combination of Sn-C bond cleavage, C-C bond formation, C-H activation and intramolecular deprotonation of a rhodium hydride intermediate, which results in methylene transfer from an SnMe group to the pincer system and PCP-chelate expansion. A methylene-transfer reaction was also demonstrated with tetramethyltin as the methylene source in the presence of KOC(CH(3))(3) at room temperature. The resulting unstable "chelate-expanded" Rh(I) complex [(C(10)H(5)(CH(2)PiPr(2))(2))(CH(2))Rh(L)] (L=N(2), THF; 4a) was isolated as its carbonyl derivative 5a. Heating 4a in benzene yielded an equimolar amount of toluene and 1a, which demonstrates the ability of the Rh(I) pincer complex to extract a methylene group from an unactivated alkyl tin substrate and transfer it, via C-C followed by C-H activation, to an arene. Use of fluorobenzene resulted in formation of fluorotoluene. Catalytic methylene-group transfer mediated by 1a was not possible, because of formation of o-xylylene complex 8 under the reaction conditions. Steric parameters play a decisive role in the reactivity with tin compounds; while iPrP derivative 1 a underwent facile reactions, tBuP complex 1b was inert.     

Metal-ligand cooperation in C-H and H2 activation by an electron-rich PNP Ir(I) system: facile ligand dearomatization-aromatization as key steps

Unusual reactions are reported, in which the aromatic PNP ligand (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) acts in concert with the metal in the activation of H2 and benzene, via facile aromatization/dearomatization processes of the ligand. A new, dearomatized electron-rich (PNP*)Ir(I) complex 2 (PNP* = deprotonated PNP) activates benzene to form the aromatic (PNP)Ir(I)Ph 4, which upon treatment with CO undergoes a surprising oxidation process to form (PNP*)Ir(III)(H)CO 6, involving proton migration from the ligand "arm" to the metal, with concomitant dearomatization. 4 undergoes stereoselective activation of H2 to exclusively form the trans-dihydride 7, rather than the expected cis-dihydride complex. Our evidence, including D-labeling, suggests the possibility that the Ir(I)-Ph complex is transformed to the dearomatized Ir(III)(Ph)(H) (independently prepared at low temperature), which may be the actual intermediate undergoing H2 activation.     

Diastereoselective formation of a dipalladium(I) complex supported by a bridging tetradentate ligand,and oxidative addition of RS-H across a phosphine-bridged Pd(I)-Pd(I) bond

The ligand CH2(P(o-C6H4NMe2)2)2 (dmapm) gives access to the first example of a dipalladium(I) complex supported by a tetradentate ligand, Pd2Cl2(mu-N,P,P,N-dmapm), which, unlike the well-known Pd2X2(mu-dppm)2 complexes (X = halide, dppm = bis(diphenylphosphino)methane), reacts with thiols to give addition of RS-H across a phosphine-bridged Pd-Pd bond.     

Nickel(0)-catalyzed isomerization of an aryne complex: formation of a dinuclear Ni(I) complex via C-H rather than C-F bond activation

The reaction of the aryne complex (PEt3)2Ni(eta2-C6H2-4,5-F2) with a catalytic amount of Ni(PEt3)2 results in a dinuclear Ni(I) complex from the coupling of the isomer (PEt3)2Ni(eta2-C6H2-3,4-F2), obtained via rearrangement of the aromatic C-H bonds, which demonstrates that Ni(PEt3)2 is kinetically capable of C-H bond activation, even in the presence of C-F bonds. The intermediate [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) was isolated and crystallographically characterized; the mu-eta2:eta2-bonding mode observed is unprecedented in aryne chemistry.     

1,4-shifts in a dinuclear Ni(I) biarylyl complex: a mechanistic study of C-H bond activation by monovalent nickel

The known aryne complex (PEt3)2Ni(eta2-C6H2-4,5-F2) (1a) reacts with a catalytic amount of Br2Ni(PEt3)2 over 1% Na/Hg to afford the dinuclear Ni(I) biarylyl complex [(PEt3)2Ni]2(mu-eta1:eta1-3,4-F2C6H2-3',4'-F2C6H2) (2a), which results from a combination of C-C bond formation and C-H bond rearrangement. The dinuclear benzyne [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) (3) was obtained by the reaction of 1a with a stoichiometric amount of Br2Ni(PEt3)2 over excess 1% Na/Hg, and 3 was found to catalyze the conversion of 1a to 2a. The reaction of 1a with B(C6F5)3 produced the trinuclear complex (PEt3)3Ni3(mu3:eta1:eta1:eta2-4,5-F2C6H2)(mu3:eta1:eta1:eta2-4,5-F2C6H2-4',5'-F2C6H2) (6). The addition of PEt3 to 6 produced 1 equiv of 1a and 1 equiv of [(PEt3)2Ni]2(mu-eta1:eta1-4,5-F2C6H2-4',5'-F2C6H2) (7a). Both 6 and 7a were identified as intermediates in the conversion of 1a to 2a. The analogue [(PEt3)(PMe3)Ni]2(mu-eta1:eta1-4,5-F2C6H2-4',5'-F2C6H2) (7b) was prepared by the addition of PMe3 to 6 and was structurally characterized. NMR spectroscopic evidence identified the additional asymmetric biarylyl [(PEt3)2Ni]2(mu-eta1:eta1-4,5-F2C6H2-3',4'-F2C6H2) (8a) during the conversion of 1a to 2a. The initial observation of 2 equiv of 8a for every equivalent of 2a produced from solutions of 7a suggests that 8a and 2a are formed from a common intermediate. A crossover labeling experiment shows that the C-H bond rearrangement steps in the conversion of 1a to 2a occur with the intermolecular scrambling of hydrogen and deuterium labels. The evidence collected suggests that Ni(I) complexes are capable of activating aromatic C-H bonds.     

Iridium(I) complex of chelating pyridine-2-thiolate ligand: Synthesis, reactivity, and application to the catalytic E-selective terminal alkyne dimerization via C-H activation

A novel iridium(I) complex bearing a chelate-coordinated pyridine-2-thiolate ligand [Ir(η²-SNC₅H₄)(PPh₃)₂] (2) was prepared by the reaction of iridium ethylene complex [IrCl(C₂H₄)(PPh₃)₂] (1) with lithium salt of pyridine-2-thiol (Li[SNC₅H₄]). On the treatment of iridium(I) complex 2 with chloroform, iridium(III) dichloro-complex [IrCl₂(η²-SNC₅H₄)(PPh₃)₂] (3) was formed. Reactions of complex 2 with methyldiphenylsilane, acetic acid, and p-tolylacetylene afforded iridium(III) hydride complexes [IrH(SiMePh₂)(η²-SNC₅H₄)(PPh₃)₂] (4), [IrH(O₂CCH₃)(η²-SNC₅H₄)(PPh₃)₂] (5), and [IrH(CC(p-tolyl))(η²-SNC₅H₄)(PPh₃)₂] (6), respectively. Complex 2 catalyzed dimerization of terminal alkynes leading to enynes (7) with high E-selectivity via C-H bond activation.     

C-H activation on a diphosphine and hydrido-bridged diiridium complex: generation and detection of an active IrII-IrII species [(Cp*Ir)2(micro-dmpm)(micro-H)]+

Reaction of [Cp*Ir(micro-H)](2) (5) (Cp* = eta(5)-C(5)Me(5)) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)(2)(micro-dmpm)(micro-H)(2)] (3). Treatment of 3 with methyl triflate at -30 degrees C results in the formation of [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Me)(IrCp*)][OTf] (6). Warming a solution of above 0 degrees C brings about predominant generation of 32e(-) Ir(II)-Ir(II) species [(Cp*Ir)(micro-dmpm)(micro-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 degrees C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(micro-Me(2)PCH(2)PMeCH(2))(micro-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C-H bond of the dmpm ligand. Intermolecular C-H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp(2) C-H activation to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(micro-dmpm)(micro-C(5)H(4)N)(H)(IrCp*)][OTf] (12), respectively. Complex also reacts with cyclopentene at 0 degrees C to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis.     

Interplay between halogen bond and lithium bond in MCN-LiCN-XCCH (M = H, Li, and Na; X = Cl, Br, and I) complex: the enhancement of halogen bond by a lithium bond

Quantum chemical calculations have been performed to study the complex of MCN-LiCN-XCCH (M = H, Li, and Na; X = Cl, Br, and I). The aim is to study the cooperative effect between halogen bond and lithium bond. The alkali metal has an enhancing effect on the lithium bond, making it increased by 77 and 94% for the Li and Na, respectively. There is the cooperativity between the lithium bond and halogen bond. The former has a larger enhancing effect on the latter, being in a range of 11.7-29.4%. The effect of cooperativity on the halogen bond is dependent on the type of metal and halogen atoms. The enhancing mechanism has been analyzed in views with the orbital interaction, charge transfer, dipole moment, polarizability, atom charges, and electrostatic potentials. The results show that the electrostatic interaction plays an important role in the enhancement of halogen bond.     

Mechanistic studies on peroxide activation by a water-soluble iron(III)-porphyrin: implications for O-O bond activation in aqueous and nonaqueous solvents

The reactions of a water-soluble iron(III)-porphyrin, [meso-tetrakis(sulfonatomesityl)porphyrinato]iron(III), [Fe(III)(tmps)] (1), with m-chloroperoxybenzoic acid (mCPBA), iodosylbenzene (PhIO), and H(2)O(2) at different pH values in aqueous methanol solutions at -35 degrees C have been studied by using stopped-flow UV/Vis spectroscopy. The nature of the porphyrin product resulting from the reactions with all three oxidants changed from the oxo-iron(IV)-porphyrin pi-cation radical [Fe(IV)(tmps(*+))(O)] (1(++)) at pH<5.5 to the oxo-iron(IV)-porphyrin [Fe(IV)(tmps)(O)] (1(+)) at pH>7.5, whereas a mixture of both species was formed in the intermediate pH range of 5.5-7.5. The observed reactivity pattern correlates with the E degrees' versus pH profile reported for 1, which reflects pH-dependent changes in the relative positions of E degrees'(Fe(IV)/Fe(III) ) and E degrees'(P(*+)/P) for metal- and porphyrin-centered oxidation, respectively. On this basis, the pH-dependent redox equilibria involving 1(++) and 1(+) are suggested to determine the nature of the final products that result from the oxidation of 1 at a given pH. The conclusions reached are extended to water-insoluble iron(III)-porphyrins on the basis of literature data concerning the electrochemical and catalytic properties of [Fe(III)(P)(X)] species in nonaqueous solvents. Implications for mechanistic studies on [Fe(P)]-catalyzed oxidation reactions are briefly addressed.