Cynthia K. Schauer

Characterization of a Rhodium(I) σ-Methane Complex in Solution

Methane Loosely Bound For the most part, molecular bonds involve sharing of electrons between two discrete atoms. In certain cases, however, a third atom can also attract a portion of the electron density without fully cleaving the bond. Such loose complexes between C-H bonds and transition metals are often invoked as short-lived intermediates in metal-catalyzed reactions of hydrocarbons, though they are rarely observed directly. Bernskoetter et al. (p. 553) glimpse this coordination motif for methane (CH4) and rhodium (Rh) using low-temperature nuclear magnetic resonance spectroscopy after protonation of an Rh-CH3 precursor. Kinetics measurements revealed a half-life of just over 80 minutes at −87°C. A loosely bound complex of rhodium and methane has been observed by low-temperature nuclear magnetic resonance spectroscopy. Numerous transition metal–mediated reactions, including hydrogenations, hydrosilations, and alkane functionalizations, result in the cleavage of strong σ bonds. Key intermediates in these reactions often involve coordination of the σ bond of dihydrogen, silanes (Si-H), or alkanes (C-H) to the metal center without full scission of the bond. These σ complexes have been characterized to varying degrees in solid state and solution. However, a σ complex of the simplest hydrocarbon, methane, has eluded full solution characterization. Here, we report nuclear magnetic resonance spectra of a rhodium(I) σ-methane complex obtained by protonation of a rhodium-methyl precursor in CDCl2F solvent at –110°C. The σ-methane complex is shown to be more stable than the corresponding rhodium(III) methyl hydride complex. Even at –110°C, methane rapidly tumbles in the coordination sphere of rhodium, exchanging free and bound hydrogens. Kinetic studies reveal a half-life of about 83 minutes at –87°C for dissociation of methane (free energy of activation is 14.5 kilocalories per mole).

Selective Electrocatalytic Reduction of CO2 to Formate by Water-Stable Iridium Dihydride Pincer Complexes

Iridium dihydride complexes supported by PCP-type pincer ligands rapidly insert CO(2) to yield κ(2)-formate monohydride products in THF. In acetonitrile/water mixtures, these complexes become efficient and selective catalysts for electrocatalytic reduction of CO(2) to formate. Electrochemical and NMR spectroscopic studies have provided mechanistic details and structures of key intermediates.

Molecular acidity: A quantitative conceptual density functional theory description.

Accurate predictions of molecular acidity using ab initio and density functional approaches are still a daunting task. Using electronic and reactivity properties, one can quantitatively estimate pKa values of acids. In a recent paper [S. B. Liu and L. G. Pedersen, J. Phys. Chem. A 113, 3648 (2009)], we employed the molecular electrostatic potential (MEP) on the nucleus and the sum of valence natural atomic orbital (NAO) energies for the purpose. In this work, we reformulate these relationships on the basis of conceptual density functional theory and compare the results with those from the thermodynamic cycle method. We show that MEP and NAO properties of the dissociating proton of an acid should satisfy the same relationships with experimental pKa data. We employ 27 main groups and first to third row transition metal-water complexes as illustrative examples to numerically verify the validity of these strong linear correlations. Results also show that the accuracy of our approach and that of the conventional method through the thermodynamic cycle are statistically similar.

The quest for stable σ-methane complexes: computational and experimental studies

A series of cationic late transition metal pincer complexes with tridentate, neutral pincer ligands and their corresponding metal methyl complexes have been investigated by density functional theory (DFT). The key calculated quantities of interest for each metal–ligand pair were the energy of the metal methyl hydride relative to the metal σ-methane complex and the methane dissociation enthalpy and free energy. A few promising pincer ligand frameworks emerged as candidates for the syntheses of σ-methane complexes with enhanced thermal stability. The calculational predictions have been tested experimentally, and new iridium and rhodium complexes of a tridentate pincer ligand, 2,6-bis(di-tert-butylphosphinito)-3,5-diphenylpyrazine (N-PONOP) have been prepared as well as a cationic palladium methyl complex with 2,6-bis(di-tert-butylphosphinito)pyridine (PONOP) and subjected to several protonation experiments. Protonation of the (N-PONOP)Ir methyl complex yielded the corresponding five-coordinate iridium(III) methyl hydride cation. Kinetic studies of the C–H bond coupling and reductive elimination have been carried out. Line broadening NMR spectroscopic techniques have been established a barrier of 7.9(1) kcal mol−1 for H–Calkyl bond coupling in the iridium(III) methyl hydride (−100 °C). A protonation of the iridium pincer complexes at the uncoordinated pyrazine-N atom was not achieved.

Origin of molecular conformational stability: Perspectives from molecular orbital interactions and density functional reactivity theory

To have a quantitative understanding about the origin of conformation stability for molecular systems is still an unaccomplished task. Frontier orbital interactions from molecular orbital theory and energy partition schemes from density functional reactivity theory are the two approaches available in the literature that can be used for this purpose. In this work, we compare the performance of these approaches for a total of 48 simple molecules. We also conduct studies to flexibly bend bond angles for water, carbon dioxide, borane, and ammonia molecules to obtain energy profiles for these systems over a wide range of conformations. We find that results from molecular orbital interactions using frontier occupied orbitals such as the highest occupied molecular orbital and its neighbors are only qualitatively, at most semi-qualitatively, trustworthy. To obtain quantitative insights into relative stability of different conformations, the energy partition approach from density functional reactivity theory is much more reliable. We also find that the electrostatic interaction is the dominant descriptor for conformational stability, and steric and quantum effects are smaller in contribution but their contributions are indispensable. Stable molecular conformations prefer to have a strong electrostatic interaction, small molecular size, and large exchange-correlation effect. This work should shed new light towards establishing a general theoretical framework for molecular stability.

Density Functional Reactivity Theory Characterizes Charge Separation Propensity in Proton-Coupled Electron Transfer Reactions

Proton-coupled electron transfer (PCET) reactions occur in many biological and artificial solar energy conversion processes. In these reactions the electron is often transferred to a site distant to the proton acceptor site. In this work, we employ the dual descriptor and the electrophilic Fukui function from density functional reactivity theory (DFRT) to characterize the propensity for an electron to be transferred to a site other than the proton acceptor site. The electrophilic regions of hydrogen bond or van der Waal reactant complexes were examined using these DFRT descriptors to determine the region of space to which the electron is most likely to be transferred. This analysis shows that in PCET reactions the electrophilic region of the reactant complex does not include the proton acceptor site.

Role of coordination geometry in dictating the barrier to hydride migration in d6 square-pyramidal iridium and rhodium pincer complexes

Syntheses of the olefin hydride complexes [(POCOP)M(H)(olefin)][BAr(f)(4)] (6a-M, M = Ir or Rh, olefin = C(2)H(4); 6b-M, M = Ir or Rh, olefin = C(3)H(6); POCOP = 2,6-bis(di-tert-butylphosphinito)benzene; BAr(f) = tetrakis(3,5-trifluoromethylphenyl)borate) are reported. A single-crystal X-ray structure determination of 6b-Ir shows a square-pyramidal coordination geometry for Ir, with the hydride ligand occupying the apical position. Dynamic NMR techniques were used to characterize these complexes. The rates of site exchange between the hydride and the olefinic hydrogens yielded ΔG(++) = 15.6 (6a-Ir), 16.8 (6b-Ir), 12.0 (6a-Rh), and 13.7 (6b-Rh) kcal/mol. The NMR exchange data also established that hydride migration in the propylene complexes yields exclusively the primary alkyl intermediate arising from 1,2-insertion. Unexpectedly, no averaging of the top and bottom faces of the square-pyramidal complexes is observed in the NMR spectra at high temperatures, indicating that the barrier for facial equilibration is >20 kcal/mol for both the Ir and Rh complexes. A DFT computational study was used to characterize the free energy surface for the hydride migration reactions. The classical terminal hydride complexes, [M(POCOP)(olefin)H](+), are calculated to be the global minima for both Rh and Ir, in accord with experimental results. In both the Rh ethylene and propylene complexes, the transition state for hydride migration (TS1) to form the agostic species is higher on the energy surface than the transition state for in-place rotation of the coordinated C-H bond (TS2), while for Ir, TS2 is the high point on the energy surface. Therefore, only for the case of the Rh complexes is the NMR exchange rate a direct measure of the hydride migration barrier. The trends in the experimental barriers as a function of M and olefin are in good agreement with the trends in the calculated exchange barriers. The calculated barriers for the hydride migration reaction in the Rh complexes are ∼2 kcal/mol higher than for the Ir complexes, despite the fact that the energy difference between the olefin hydride ground state and the agostic alkyl structure is ∼4 kcal/mol larger for Ir than for Rh. This feature, together with the high barrier for interchange of the top and bottom faces of the complexes, is proposed to arise from the unique coordination geometry of the agostic complexes and the strong preference for a cis-divacant octahedral geometry in four-coordinate intermediates.

Highly polydentate ligands. Part 4. Crystal structures of neodymium(III) and erbium(III) complexes of 3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedioate(4–)

The structures of calcium salts of the erbium(III) and neodymium(III) chelates of the calcium-selective octadentate ligand egta4–[H4egta = 3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedioic acid] have been determined, in order to identify the structural changes that occur in a calcium-selective binding site when lanthanides are substituted for calcium. Ca[Er(egta)(OH2)]2·12H2O·(CH3)2CO (1) crystallizes in the monoclinic space group P21(Z= 2), with a= 12.710(2), b= 12.157(2), c= 17.765(3)A, and β= 105.79(1)°R= 0.027, R′= 0.035. Ca[Nd(egta)(OH2)]2·9H2O (2) crystallizes in the monoclinic space group P21/c(Z= 2), with a= 10.776(2), b= 18.218(4), c= 12.560(2)A, and β= 112.14(1)°; R= 0.028, R′= 0.040. The full octadentate chelating capability of egta4– is utilized in both chelates. In contrast to the eight-co-ordinate calcium ions in [Ca(egta)]2–, the ErIII ions in (1) are nine-co-ordinate; the ninth co-ordination site is occupied by a water molecule. Of the three ligand atom types, the carboxylate oxygen atoms are bound at the shortest distance [Er–O(carboxylate)av= 2.31(3)A], followed by the ether oxygen atoms [Er–O(ether)av= 2.42(5)A], and the amine nitrogen atoms [Er–Nav= 2.57(4)A]. The NdIII ions in (2) are ten-co-ordinate; ten-co-ordination is achieved in the solid state by binding a water molecule, as well as a carboxylate oxygen atom from an adjacent complex ion The order of metal–Iigand bond distances observed for NdIII is the same as that observed for ErIII Nd–O(carboxylate)av= 2.46(1), Nd–O(ether)av= 2.67(3), Nd–Nav= 2.81(7)A.

Crystal and molecular structure of an N-arylporphyrin complex: Chloro(N-phenyl-5,10,15,20-tetraphenylporphinato)-zinc(II)

Caracteristiques de la structure moleculaire (absorption visible et spectre RMN de 1 H) du chloro(N-phenyl-tetraphenyl-5, 10, 15, 20 porphinato)-zinc (II), et comparaison des parametres du site de coordination et du noyau de porphyrine, avec ceux des complexes de zinc (II) N-methyl correspondants, et ceux des complexes N-methylporphyrine

Ring-Slippage and Multielectron Redox Properties of Fe/Ru/Os–Bis(arene) Complexes: Does Hapticity Change Really Cause Potential Inversion?

Bis(hexamethylbenzene) complexes of the group 8 metals (Fe, Ru, Os) show surprising diversity in their electron-transfer mechanisms and associated thermodynamics for the M(II) → M(I) → M(0) redox series. In electrochemical experiments, the Fe complex exhibits normally ordered potentials separated by ∼1 V, the Ru system shows nearly overlapping one-electron redox events, and Os demonstrates a one-step, two-electron transfer with a peak potential separation suggestive of highly inverted potentials. It has been conjectured that the sequential one-electron transfers observed for Fe are due to the lack of an accessible η(4):η(6) Fe(0) state, destabilizing the fully reduced species. Using an established model chemistry based on DFT, we demonstrate that the hapticity change is a consequence of the bonding throughout this transition metal triad and that apparent multielectron behavior is controlled by the vertical electron attachment component of the M(II) → M(I) redox event. Furthermore, the η(6):η(6) Fe(0) triplet state is more favorable than the hypothetical η(4):η(6) singlet state, emphasizing that the hapticity change is not sufficient for multielectron behavior. Despite both displaying two-electron redox responses, Ru and Os traverse fundamentally different mechanisms based on whether the first (Os) or second (Ru) electron transfer induces the hapticity change. While the electronic structure analysis is limited to the Fe triad here, the conceptual model that we developed provides a general understanding of the redox behavior exhibited by d(6) bis(arene) compounds.