An electronic perspective on the reduction of an n=n double bond at a conserved dimolybdenum core

Density functional theory has been used to assess the role of the bimetallic core in supporting reductive cleavage of the N=N double bond in [Cp2Mo2(mu-SMe)3(mu-eta1:eta1-HN=NPh)]+. The HOMO of the complex, the Mo-Mo delta orbital, plays a key role as a source of high-energy electrons, available for transfer into the vacant orbitals of the N=N unit. As a result, the metal centres cycle between the Mo(III) and Mo(IV) oxidation states. The symmetry of the Mo-Mo delta "buffer" orbital has a profound influence on the reaction pathway, because significant overlap with the redox-active orbital on the N=N unit (pi* or sigma*) is required for efficient electron transfer. The orthogonality of the Mo-Mo delta and N-N sigma* orbitals in the eta1:eta1 coordination mode ensures that electron transfer into the N-N sigma bond is effectively blocked, and a rate-limiting eta1:eta1-->eta1 rearrangement is a necessary precursor to cleavage of the bond.     

Nitrogen fixation under mild ambient conditions: part I--the initial dissociation/association step at molybdenum triamidoamine complexes

In several recent studies Schrock and collaborators demonstrated for the first time how molecular dinitrogen can be catalytically transformed under mild and ambient conditions to ammonia by a molybdenum triamidoamine complex. In this work, we investigate the geometrical and electronic structures involved in this process of dinitrogen activation with quantum chemical methods. Density functional theory (DFT) has been employed to calculate the coordination energies of ammonia and dinitrogen relevant for the dissociation/association step in which ammonia is substituted by dinitrogen. In the DFT calculations the triamidoamine chelate ligand has been modeled by a systematic hierarchy of increasingly complex substituents at the amide nitrogen atoms. The most complex ligand considered is an experimentally known ligand with an HMT = 3,5-(2,4,6-Me3C6H2)2C6H3 substituent. Several assumptions by Schrock and collaborators on key reaction steps are confirmed by our calculations. Additional information is provided on many species not yet observed experimentally. Particular attention is paid to the role of the charge of the complexes. The investigation demonstrates that dinitrogen coordination is enhanced for the negatively charged metal fragment, that is, coordination is more favorable for the anionic metal fragment than for the neutral species. Coordination of N2 is least favorable for the cationic metal fragment. Furthermore, ammonia abstraction from the cationic complex is energetically unfavorable, while NH3 abstraction is less difficult from the neutral and easily feasible from the anionic low-spin complex.     

Energetics and mechanism of ammonia synthesis through the Chatt Cycle: conditions for a catalytic mode and comparison with the Schrock Cycle

Through a series of DFT calculations the energy profile of the Chatt cycle is evaluated. This is the counterpiece of our earlier investigations of the Schrock cycle (Angew. Chem. 2005, 117, 5783; Angew. Chem. Int. Ed. 2005, 44, 5639), applying the same quantumchemical methodology and approximations. As for the Schrock cycle, decamethylchromocene acts as reductant. The protonation reactions are considered to be mediated by HBF4/diethyl ether or lutidinium. For all protonation and reduction steps the corresponding free reaction enthalpy changes are calculated. The derived energy profile and corresponding reaction mechanism bear strong similarities to the Schrock cycle. In particular, the most endergonic reaction is the first protonation of the N2 complex and the most exergonic reaction is the cleavage of the N--N bond. If lutidinium is employed as acid and Cp2*Cr as reductant, the reaction course involves steps that are not thermally allowed. For HBF4/diethyl ether as the acid and Cp2*Cr as reducant, however, a catalytic cycle consisting of thermally allowed reactions is principally feasible. This cycle involves a Mo I-fluoro complex as dinitrogen intermediate. It is shown that regeneration to the Mo 0-bis(dinitrogen) complex is thermally not accessible in this system. Moreover, the Mo I fluoro-dinitrogen complex is labile towards disproportionation. The implications of these results with respect to the realization of a catalytic system on the basis of Mo and W phosphine complexes are discussed.     

Palladium–N‐Heterocyclic Carbene (NHC)‐Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp3)H Activation: Scope and DFT Study

Two bulky, chiral, monodentate N‐heterocyclic carbene ligands were applied to palladium‐catalyzed asymmetric C?H arylation to incorporate C(sp³)?H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans‐2,3‐substituted indolines. Although this C_Ar?C_alkyl coupling requires high temperatures (140–160 °C), chiral induction is high. This regiodivergent reaction, when carried out with enantiopure starting materials, can lead to single structurally different enantiopure products, depending on the catalyst chirality. The C?H activation at a tertiary center was realized only in the case of a cyclopropyl group. No C?H activation takes place alpha to a tertiary center. A detailed DFT study is included and analyses of methyl versus methylene versus methine C?H activation is used to rationalize experimentally observed regio‐ and enantioselectivities.     

NH3 Synthesis in the N2/H2 Reaction System using Cooperative Molecular Tungsten/Rhodium Catalysis in Ionic Hydrogenation: A DFT Study

The ionic hydrogenation of N₂ with H₂ to give NH₃ is investigated by means of density functional theory (DFT) computations using a cooperatively acting catalyst system. In this system, N₂ binds to a neutral tungsten pincer complex of the type [(PNP)W(N₂)₃] (PNP=pincer ligand) and is reduced to NH₃. The protons and hydride centers necessary for the reduction are delivered by heterolytic cleavage of H₂ between the N₂–tungsten complex and the cationic rhodium complex [Cp*Rh{2‐(2‐pyridyl)phenyl}(CH₃CN)]⁺. Successive transfer of protons and hydrides to the bound N₂, as well as all N_xH_y units that occur during the reaction, enable the computation of closed catalytic cycles in the gas and in the solvent phase. By optimizing the pincer ligands of the tungsten complex, energy spans as low as 39.3 kcal mol^?1 could be obtained, which is unprecedented in molecular catalysis for the N₂/H₂ reaction system.     

Cobalt‐Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Reaction Conditions

The first successful example of cobalt‐catalyzed reduction of N₂ with Me₃SiCl and Na as a reductant, under ambient reaction conditions, gives N(SiMe₃)₃, which can be readily converted into NH₃. In this reaction system, 2,2′‐bipyridine (bpy) is found to work as an effective additive to improve substantially the catalytic activity. Co?N₂ complexes bearing three Me₃Si groups as ancillary ligands are considered to work as key reactive species based on DFT calculations. The DFT results also allow the proposal of a detailed reaction pathway for the transformation of N₂ into N(SiMe₃)₃.     

A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes

A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi* orbital upon electronic excitation from the singlet ground state S0 to the first excited singlet state S1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S1 state and approaches its minimum structure in the S1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These protonated thiolate functionalities bring protons close to the dinitrogen moiety. Because protonation does not change the pi*-antibonding character of the LUMO, the universal and well-directed character of the photochemical activation process makes it possible to protonate the dinitrogen complex before it is irradiated. The pi*-antibonding LUMO plays the central role in the activation process, since the diazenoid structure was obtained by excitation from various occupied orbitals as well as by a direct two-electron reduction (without photochemical activation) of the complex; that is, the important bending of N2 towards a diazenoid conformation can be achieved by populating the pi*-antibonding LUMO.     

Tracing the Route to Ammonia: A Theoretical Study on the Possible Pathways for Dinitrogen Reduction with Tripodal Iron Complexes

The chemistry of nitrogen fixation has been the subject of considerable research with a view to gaining a proper understanding of the mechanistic details. In this article, density functional calculations are performed on all the mechanistic possibilities for dinitrogen reduction mediated by the tripodal iron complexes [(SiP^Me₃)Fe^I] ( [Fe_Si] ) and [(BP^Me₃)Fe⁰] ( [Fe_B] ). Dinitrogen addition to the neutral bare complex is found to be thermodynamically more favorable than that to the anionic one. Both symmetric and asymmetric pathways, along with the possible intermediates and transition states, are considered in this study. For both systems, the symmetric path is found to be more likely, although the prospect of the asymmetric path cannot be ignored. Moreover, interconversions between these two pathways are found to be less likely. This study corroborates most experimental observations and provides theoretical insight into the possible existence of some hitherto unknown intermediates such as multiple‐bonded Fe? N species in a trigonal bipyramidal geometry. Furthermore, in agreement with experimental observations, this study also highlights the possibility of hydrogen and hydrazine evolution during the complete reduction of dinitrogen.     

New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility

Our aim is to understand the electronic and steric factors that determine the activity and selectivity of transition‐metal catalysts for cross‐coupling reactions. To this end, we have used the activation strain model to quantum‐chemically analyze the activity of catalyst complexes d¹⁰‐M(L)_n toward methane C?H oxidative addition. We studied the effect of varying the metal center M along the nine d¹⁰ metal centers of Groups 9, 10, and 11 (M=Co^?, Rh^?, Ir^?, Ni, Pd, Pt, Cu⁺, Ag⁺, Au⁺), and, for completeness, included variation from uncoordinated to mono‐ to bisligated systems (n=0, 1, 2), for the ligands L=NH₃, PH₃, and CO. Three concepts emerge from our activation strain analyses: 1) bite‐angle flexibility, 2) d‐regime catalysts, and 3) s‐regime catalysts. These concepts reveal new ways of tuning a catalyst’s activity. Interestingly, the flexibility of a catalyst complex, that is, its ability to adopt a bent L‐M‐L geometry, is shown to be decisive for its activity, not the bite angle as such. Furthermore, the effect of ligands on the catalyst’s activity is totally different, sometimes even opposite, depending on the electronic regime (d or s) of the d¹⁰‐M(L)_n complex. Our findings therefore constitute new tools for a more rational design of catalysts.     

Ruthenium‐Catalyzed Oxidative Coupling of Primary Amines with Internal Alkynes through CH Bond Activation: Scope and Mechanistic Studies

The oxidative coupling of primary amines with internal alkynes catalyzed by Ru complexes is presented as a general atom‐economy methodology with a broad scope of applications in the synthesis of N‐heterocycles. Reactions proceed through regioselective C?H bond activation in 15 minutes under microwave irradiation or in 24 hours with conventional heating. The synthesis of 2,3,5‐substituted pyridines, benzo[h]isoquinolines, benzo[g]isoquinolines, 8,9‐dihydro‐benzo[de]quinoline, 5,6,7,8‐tetrahydroisoquinolines, pyrido[3,4g]isoquinolines, and pyrido[4,3g]isoquinolines is achievable depending on the starting primary amine used. DFT calculations on a benzylamine substrate support a reaction mechanism that consists of acetate‐assisted C?H bond activation, migratory‐insertion, and C?N bond formation steps that involve 28–30 kcal mol^?1. The computational study is extended to additional substrates, namely, 1‐naphthylmethyl‐, 2‐methylallyl‐, and 2‐thiophenemethylamines.     

Dinitrogen Activation by Fryzuk’s [Nb(P2N2)] Complex and Comparison with the Laplaza–Cummins [Mo{N(R)Ar}3] and Schrock [Mo(N3N)] Systems

The reaction profile of N₂ with Fryzuk’s [Nb(P₂N₂)] (P₂N₂=PhP(CH₂SiMe₂NSiMe₂CH₂)₂PPh) complex is explored by density functional calculations on the model [Nb(PH₃)₂(NH₂)₂] system. The effects of ligand constraints, coordination number, metal and ligand donor atom on the reaction energetics are examined and compared to the analogous reactions of N₂ with the three‐coordinate Laplaza‐Cummins [Mo{N(R)Ar}₃] and four‐coordinate Schrock [Mo(N₃N)] (N₃N=[(RNCH₂CH₂)₃N]^3?) systems. When the model system is constrained to reflect the geometry of the P₂N₂ macrocycle, the N? N bond cleavage step, via a N₂‐bridged dimer intermediate, is calculated to be endothermic by 345 kJ mol^?1. In comparison, formation of the single‐N‐bridged species is calculated to be exothermic by 119 kJ mol^?1, and consequently is the thermodynamically favoured product, in agreement with experiment. The orientation of the amide and phosphine ligands has a significant effect on the overall reaction enthalpy and also the N? N bond cleavage step. When the ligand constraints are relaxed, the overall reaction enthalpy increases by 240 kJ mol^?1, but the N₂ cleavage step remains endothermic by 35 kJ mol^?1. Changing the phosphine ligands to amine donors has a dramatic effect, increasing the overall reaction exothermicity by 190 kJ mol^?1 and that of the N? N bond cleavage step by 85 kJ mol^?1, making it a favourable process. Replacing Nb^II with Mo^III has the opposite effect, resulting in a reduction in the overall reaction exothermicity by over 160 kJ mol^?1. The reaction profile for the model [Nb(P₂N₂)] system is compared to those calculated for the model Laplaza and Cummins [Mo{N(R)Ar}₃] and Schrock [Mo(N₃N)] systems. For both [Mo(N₃N)] and [Nb(P₂N₂)], the intermediate dimer is calculated to lie lower in energy than the products, although the final N? N cleavage step is much less endothermic for [Mo(N₃N)]. In contrast, every step of the reaction is favourable and the overall exothermicity is greatest for [Mo{N(R)Ar}₃], and therefore this system is predicted to be most suitable for dinitrogen cleavage.