Theoretical Study on the Mechanism of the Hydrogenation of Azo (N═N) Bonds to Amines Catalyzed by Manganese.

The mechanism of the transition metal manganese complex Mn(PhPNN)(CO)2Br (CA-4) that catalyzed the hydrogenation of the azo (N═N) bond to amines has been investigated using the PBE0 function. The results show that the whole reaction involves three basic processes: (1) the addition of H2 to CA gives IN2, which can hydrogenate the azo (N═N) bond at the later stage; (2) hydrogenation of azobenzene by IN2, which gives 1,2-diphenylhydrazine (PhNHNHPh); and (3) hydrogenation of 1,2-diphenylhydrazine by IN2, which affords aniline (PhNH2). The results suggest that the hydrogenation of CA and hydrogenation of azobenzene by IN2 to afford PhNHNHPh are easy to occur due to the low barriers, and the overall rate-determining step is the formation of IN11 and PhNH2 by breaking the N-N bond in the stage of hydrogenation of 1,2-diphenylhydrazine by IN2, with an energy barrier of 39.1 kcal/mol. The computed results are in good agreement with the experimental results. The mechanism of the azobenzene reaction catalyzed by manganese was analyzed by charge and orbital analysis in detail. The theoretical results provide a deeper understanding of the mechanism and fully explain the experimental facts.

Fluorescence enhancement of surface plasmon coupled emission by Au nanobipyramids and its modulation effect on multi-wavelength radiation.

Surface plasmon coupled emission (SPCE), a novel surface-enhanced fluorescence technique, can generate directional and amplified radiation by the intense interaction between fluorophores and surface plasmons (SPs) of metallic nanofilms. For plasmon-based optical systems, the strong interaction between localized and propagating SPs and "hot spot" structures show great potential to significantly improve the electromagnetic (EM) field and modulate optical properties. Au nanobipyramids (NBPs) with two sharp apexes to enhance and restrict the EM field were introduced through electrostatic adsorption to achieve a mediated fluorescence system, and the emission signal enhancement was realized by factors over 60 compared with the normal SPCE. It has been demonstrated that the intense EM field produced by the NBPs assembly is what triggered the unique enhancement of SPCE by Au NBPs, which effectively overcomes the inherent signal quenching of SPCE for ultrathin sample detection. This remarkable enhanced strategy offers the chance to improve the detection sensitivity for plasmon-based biosensing and detection systems, and expand the range of applications for SPCE in bioimaging with more comprehensive and detailed information acquisition. The enhancement efficiency for various emission wavelengths was investigated in light of the wavelength resolution of SPCE, and it was discovered that enhanced emission for multi-wavelength could be successfully detected through the different emission angles due to the angular displacement caused by wavelength change. Benefit from this, the Au NBP modulated SPCE system was employed for multi-wavelength simultaneous enhancement detection under a single collection angle, which could broaden the application of SPCE in simultaneous sensing and imaging for multi-analytes, and expected to be used for high throughput detection of multi-component analysis.

Amplified Fluorescence by Hollow-Porous Plasmonic Assembly: A New Observation and Its Application in Multiwavelength Simultaneous Detection.

Surface plasmon coupled emission (SPCE) is a new analytical technique that provides increased and directional radiation based on the near-field interaction between fluorophores and surface plasmons but suffers from the limitation of insufficient sensitivity. The assembly of hollow-porous plasmonic nanoparticles could be the qualified candidate. After the introduction of gold nanocages (AuNCs), fluorescence signal enhancement was realized by factors over 150 and 600 compared with the normal SPCE and free space emission, respectively, with a fluorophore layer thickness of approximately 10 nm; hence, the unique enhancement of SPCE by the AuNCs effectively overcomes the signal quenching induced by resonance energy transfer (in normal SPCE). This enhancement was proven to be triggered by the superior wavelength match, the enhanced electromagnetic field, and new radiation channel and process induced by the AuNC assembly, which provides an opportunity to increase the detection sensitivity and establish an optimal plasmonic enhancement system. The amplified SPCE system was employed for multiwavelength simultaneous enhancement detection through the assembly of mixed hollow nanoparticles (AuNCs and gold nanoshells), which could broaden the application of SPCE in simultaneous sensing and imaging for multianalytes.

Computational Insight into the Mechanism of Ruthenium(II)-Catalyzed α-Alkylation of Arylmethyl Nitriles Using Alcohols.

The ruthenium(II)-catalyzed α-alkylation reaction of arylmethyl nitriles (phenylacetonitrile) using alcohols (ethanol) in toluene has been extensively investigated by means of SMD-M06-2X/6-311G(d,p)-LANL2dz (LAnL2dz for Ru, 6-311G(d,p) for other atoms) calculations. Detailed mechanistic schemes have been proposed and discussed. The catalytically active Ru(II) complex was generated by the base-induced KCl elimination from the catalyst precursor [(PNPPh)RuHCl(CO)]. The overall Ru(II) catalytic cycle consists of three basic processes: (1) ethanol-to-aldehyde transformation catalyzed by the 16-electron unsaturated ruthenium pincer catalyst; (2) a 16-electron unsaturated ruthenium pincer catalyst catalyzed condensation reaction of arylmethyl nitrile with aldehyde, which leads to PhC(CN)=CHCH3; (3) hydrogenation of PhC(CN)=CHCH3, which leads to the formation of the α-alkylated arylmethyl nitrile product (PhCH(CH2CH3)CN). The DFT results revealed that the rate-determining barrier of the overall reaction was 23.9 kcal/mol of the H-transfer step in the third process. The reaction of PhC(CN)=CHCH3 with the dihydride Ru complex, which is generated in the ethanol-to-aldehyde transformation process, is the more preferable hydrogenation mechanism than hydrogenation of vinyl nitrile-Ru complex by H2. Using alcohol as the reactant not only fulfills the requirement of the borrowing-H strategy but also lowers the barriers of the H-migration steps.

The mechanisms for N-heterocyclic olefin-catalyzed formation of cyclic carbonate from CO2 and propargylic alcohols.

The mechanistic details of N-heterocyclic olefin-catalyzed formation of cyclic carbonate from CO2 and propargylic alcohols were investigated by DFT calculations. Six mechanisms, four for the formation of five-membered cyclic carbonate (M-A, M-B, M-B' and M-C), and two for six-membered cyclic carbonate (M-D and M-E), were fully investigated. The energy profiles in dichloromethane showed that M-B is the predominant reaction with the lowest barrier of 31.99 kcal mol(-1), while M-C and M-D may be kinetically competitive to M-B. The very high activation energy of 45.37 kcal mol(-1), 57.07 kcal mol(-1) and 59.61 kcal mol(-1) for M-A, M-B' and M-E, respectively, suggest that they are of lesser importance in the overall mechanism.

Direct ab initio study on the rate constants of radical C2(A 3Π(u)) + C3H8 reaction.

The mechanism and kinetics of the radical (3)C(2) + C(3)H(8) reaction have been investigated theoretically by direct ab initio kinetics over a wide temperature range. The potential energy surfaces have been constructed at the CCSD(T)/B3//UMP2/B1 levels of theory. The electron transfer was also analyzed by quasi-restricted orbital (QRO) in detail. It was shown that all these channels proceed exclusively via hydrogen abstraction. The overall ICVT/SCT rate constants are in agreement with the available experimental results. The prediction shows that the secondary hydrogen of C(3)H(8) abstraction by (3)C(2) radical is the major pathway at low temperatures (below 700 K), while as the temperature increases, the primary hydrogen of C(3)H(8) abstraction becomes more important and more favorable. A negative temperature dependence of the rate constants for the reaction of (3)C(2) + C(3)H(8) was observed. The three-(k (3)) and four-parameter (k (4)) rate-temperature expressions were also provided within 243-2000 K to facilitate future experimental studies.

Mechanism insights of ethane C-H bond activations by bare [Fe(III)═O]+: explicit electronic structure analysis.

Alkane C-H bond activation by various catalysts and enzymes has attracted considerable attention recently, but many issues are still unanswered. The conversion of ethane to ethanol and ethene by bare [Fe(III)═O](+) has been explored using density functional theory and coupled-cluster method comprehensively. Two possible reaction mechanisms are available for the entire reaction, the direct H-abstraction mechanism and the concerted mechanism. First, in the direct H-abstraction mechanism, a direct H-abstraction is encountered in the initial step, going through a collinear transition state C···H···O-Fe and then leading to the generation of an intermediate Fe-OH bound to the alkyl radical weakly. The final product of the direct H-abstraction mechanism is ethanol, which is produced by the hydroxyl group back transfer to the carbon radical. Second, in the concerted reaction mechanism, the H-abstraction process is characterized via overcoming four/five-centered transition states (6/4)TSH_c5 or (4)TSH_c4. The second step of the concerted mechanism can lead to either product ethanol or ethene. Moreover, the major product ethene can be obtained through two different pathways, the one-step pathway and the stepwise pathway. It is the first report that the former pathway starting from (6/4)IM_c to the product can be better described as a proton-coupled electron transfer (PCET). It plays an important role in the product ethene generation according to the CCSD(T) results. The spin-orbital coupling (SOC) calculations demonstrate that the title reaction should proceed via a two-state reactivity (TSR) pattern and that the spin-forbidden transition could slightly lower the rate-determining energy barrier height. This thorough theoretical study, especially the explicit electronic structure analysis, may provide important clues for understanding and studying the C-H bond activation promoted by iron-based artificial catalysts.

Direct ab initio dynamics study of radical C4H (X̃2Σ+) + CH4 reaction.

The methane (CH(4)) hydrogen abstraction reaction by linear butadiynyl radical C(4)H (CCCCH) has been investigated by direct ab initio dynamics over a wide temperature range of 100-3000 K, theoretically. The potential energy surfaces (PESs) have been constructed at the CCSD(T)/aug-cc-pVTZ//BB1K/6-311G(d,p) levels of theory. Two different hydrogen abstraction channels by C(1) and C(4) of C(4)H (C(1)C(2)C(3)C(4)H) have been considered. The results indicate that the C(1) position of C(4)H is a more reactive site. The electron transfer behaviors of two possible channels are also analyzed by quasi-restricted orbital (QRO) in detail. The rate constants calculated by canonical variational transition-state theory (CVT) with the small-curvature tunneling correction (SCT) are in excellent agreement with available experimental values. The normal and three-parameter expressions of Arrhenius rate constants are also provided within 100-3000 K. It is expected to be helpful for further studies on the reaction dynamics behaviors over a wide temperature range where no experimental data is available so far.