Ligand substitution behavior of a simple model for coenzyme B12

The ligand substitution reactions of trans-[CoIII(en)2(Me)H2O]2+, a simple model for coenzyme B12, were studied for cyanide and imidazole as entering nucleophiles. It was found that these nucleophiles displace the coordinated water molecule trans to the methyl group and form the six-coordinate complex trans-[Co(en)2(Me)L]. The complex-formation constants for cyanide and imidazole were found to be (8.3 +/- 0.7) x 10(4) and 24.5 +/- 2.2 M-1 at 10 and 12 degrees C, respectively. The second-order rate constants for the substitution of water were found to be (3.3 +/- 0.1) x 10(3) and 198 +/- 13 M-1 s-1 at 25 degrees C for cyanide and imidazole, respectively. From temperature and pressure dependence studies, the activation parameters delta H++, delta S++, and delta V++ for the reaction of trans-[CoIII(en)2(Me)H2O]2+ with cyanide were found to be 50 +/- 4 kJ mol-1, 0 +/- 16 J K-1 mol-1, and +7.0 +/- 0.6 cm3 mol-1, respectively, compared to 53 +/- 2 kJ mol-1, -22 +/- 7 J K-1 mol-1, and +4.7 +/- 0.1 cm3 mol-1 for the reaction with imidazole. On the basis of reported activation volumes, these reactions follow a dissociative mechanism in which the entering nucleophile could be weakly bound in the transition state.     

Selective diphosphine ligand chelation and pi bond coordination in CoRu(CO)7(mu-PPh2): kinetics and X-ray structure of CoRu(CO)4(mu-bma)(mu-PPh2)

Thermolysis of CoRu(CO)7(mu-PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(mu-P-P)(mu-PPh2) [where P-P = bma (3a), bpcd (3b)] along with trace amounts of the known complex CoRu(CO)6(PPh3)(mu-PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(mu-P-P)(mu-PPh2) [where P-P = bma (2a), bpcd (2b)] have been prepared by separate routes (mild thermolysis and Me3NO activation) and studied for their conversion to CoRu(CO)4(mu-P-P)(mu-PPh2). The penta- and tetracarbonyl complexes have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2a-->3a and of 2b-->3b were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters (2a-->3a, delta H++ = 29.2 +/- 1.4 kcal mol-1 and delta S++ = 8.2 +/- 3.8 eu; 2b-->3b, delta H++ = 27.7 +/- 0.6 kcal mol-1 and delta S++ = 1.4 +/- 1.6 eu), a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(mu-bma)(mu-PPh2) (3a), as determined by X-ray crystallography, reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride pi bond is coordinated to the cobalt atom.     

Entropy effects in the fragmentation of 1,1-dimethylhydrazine ions

The 1,1-dimethylhydrazine ion ((CH3)2NNH2+*) has two low-energy dissociation channels, the loss of a hydrogen atom to form the fragment ion m/z 59, (CH3)(CH2)NNH2+, and the loss of a methyl radical to form the fragment ion m/z 45, the methylhydrazyl cation, CH3NNH2+. The dissociation of the 1,1-dimethylhydrazine ion has been investigated using threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy, in the photon energy range 8.25-31 eV, and tandem mass spectrometry. Theoretical breakdown curves have been obtained from a variational transition state theory (VTST) modeling of the two reaction channels and compared to those obtained from experiment. Seven transition states have been found at the B3-LYP/6-31+G(d) level of theory for the methyl radical loss channel in the internal energy range of 2.32-3.56 eV. The methyl loss channel transition states are found at R(N-C) = 4.265, 4.065, 3.965, 3.165, 2.765, 2.665, and 2.565 A over this internal energy range. Three transition states have been found for the hydrogen atom loss channel: R(H-C) = 2.298, 2.198, and 2.098 A. The DeltaS++(45) value, at an internal energy of 2.32 eV and a bond distance of R(N-C) = 4.265 A, is 65 J K-1 mol-1. As the internal energy increases to 3.56 eV the variational transition state moves to lower R value so that at R(N-C) = 2.565 A, the DeltaS++ decreases to 29 J K-1 mol-1. For the hydrogen atom loss channel the variation in DeltaS++ is less than that for the methyl loss channel. To obtain agreement with the experimental breakdown curves, DeltaS++(59) = 26-16 J K-1 mol-1 over the studied internal energy range. The 0 K enthalpies of formation (DeltafH0) for the two fragment ions m/z 45 and m/z 59 have been calculated from the 0 K activation energies (E0) obtained from the fitting procedure: DeltafH0[CH3NNH2+] = 906 +/- 6 kJ mol-1 and DeltafH0[(CH3)(CH2)NNH2+] = 822 +/- 7 kJ mol-1. The calculated G3 values are DeltafH0[CH3NNH2+] = 911 kJ mol-1 and DeltafH0[(CH3)(CH2)NNH2+] = 825 kJ mol-1. In addition to the two low-energy dissociation products, 21 other fragment ions have been observed in the dissociation of the 1,1-dimethylhydrazine ion as the photon energy was increased. Their appearance energies are reported.     

Mechanism of the interconversions between C- and N-bound transition metal alpha-cyanocarbanions

The first presentation of the intra- and intermolecular mechanisms of the C-N interconversions of transition metal alpha-cyanocarbanions is described. A pair of N- and C-bound isomers of isonitrile complex Ru+Cp(NCCH-SO2Ph)(PPh3)(CN-t-Bu) (1) and RuCp[CH(CN)SO2Ph](PPh3)(CN-t-Bu) (2) was synthesized for the mechanistic studies on the N-to-C isomerizations. Structural characterization by X-ray diffractions of 1 and 2 indicated their typical zwitterionic and alpha-metalated structures. The kinetic studies on the irreversible isomerization of 1 to 2 in benzene-d6 at 333-348 K were carried out using 1H NMR spectroscopy, affording the first-order rate constants k1 and the activation parameters DeltaH = 107 +/- 2 kJ.mol-1 and DeltaS = -22 +/- 5 J.K-1.mol-1. The almost identical values of k1 were obtained upon similar treatment of 1 with 4 equiv of external ligands such as PPh3, CH3CN, and t-BuNC at 333 K, indicating that the N-to-C isomerization proceeds in an intramolecular manner without dissociation of a ligand. As a model system for the C-to-N isomerization, the irreversible transformation of RuCp[CH(CN)SO2Ph](PPh3)2 (3) to Ru+Cp(NCCH-SO2Ph)(PPh3)2 (4) was investigated under various reaction conditions. The reaction of 3 at room temperature in THF affords the coordination dimers (RRu*,SC*,RRu*,SC*)-{RuCp[CH(CN)SO2Ph](PPh3)}2 (5) stereoselectively, and its distorted mu2-C,N-bound structure was determined by X-ray analysis. The reaction profiles for the isomerization of 3 includes the generation- and temperature-dependent decays of dimeric species 5 and its diastereomer 6, which strongly suggests that the intra- and intermolecular pathways are included in the C-to-N isomerization. The intramolecular process of the C-to-N isomerization of 3 has been confirmed by the kinetic studies on the isomerization of 3 with excess amount of PPh3 in benzene-d6 at 333-348 K which afford the first-order kinetics with the activation parameters of DeltaH = 121 +/- 1 kJ.mol-1 and DeltaS = 42 +/- 4 J.K-1.mol-1. Treatment of 5 with PPh3 in boiling benzene gives rise to the quantitative formation of N-bound complex 4. The controlled kinetic experiments on the cleavage of 5 with PPh3 have concluded that the cleavage of 5 with PPh3 proceeds via simultaneous C-Ru and N-Ru bond scissions, indicating the temperature-dependent participation of intermolecular process in the C-to-N isomerization of 3.     

Kinetics and thermodynamics of the reaction of deoxyhemerythrin with nitric oxide

Deoxyhemerythrin reacts with NO to form a 1:1 adduct shown spectrophotometrically. The kinetics of the formation have been studied directly by stopped-flow measurements at four different temperatures (0.0-23.6 degrees C). The kinetics of the dissociation have been studied, also by stopped-flow techniques, at five different temperatures (4.0-35.1 degrees C) using three different scavengers [Fe(II)(edta)2-, O2 and sperm whale deoxymyoglobin], which gave similar values. For the formation kf = (4.2 +/- 0.2) x 10(6) M-1 s-1, delta Hf not equal = 44.3 +/- 2.3 kJ mol-1, delta Sf not equal to = 30 +/- 8 J mol-1 K-1 and for the dissociation kd = 0.84 +/- 0.02 s-1, delta Hd not equal to 95.6 +/- 2.1 kJ mol-1 delta Sd not equal to = 74 +/- 7 J mol-1 K-1 (25 degrees C, I = 0.2 M and pH 7-8.1). From the kinetic data the thermodynamic data for the formation of HrNO were calculated: Kf = (5.0 +/- 0.3) x 10(6) M-1, delta H = -51.3 +/- 3.1 kJ mol-1 and delta S = -44 +/- 11 J mol-1 K-1 (25 degrees C). The kinetic data suggest that NO occupies the same iron(II) site in deoxyhemerythrin as oxygen does. The equilibrium constant for the formation of Fe(II)(edta)(NO)2- has been redetermined: K1 = (1.45 +/- 0.07) x 10(7) M-1, delta H = -77.5 +/- 1.5 kJ and mol-1 and delta S = -123.5 J mol-1 K-1 (25 degrees C).     

Kinetic and computational study of dissociative substitution and phosphine exchange at tetrahedrally distorted cis-Pt(SiMePh2)2(PMe2Ph)2

The substitution kinetics of Me2PhP in cis-Pt(SiMePh2)2(PMe2Ph)2 (1) by the chelating ligand bis(diphenylphosphino)ethane has been followed at 25.0 degrees C in dichloromethane by stopped-flow spectrophotometry. Addition of the leaving ligand causes mass-law retardation compatible with a dissociative process via a three-coordinate transition state or intermediate. Exchange of Me2PhP in 1 has been studied by variable-temperature magnetization transfer 1H NMR in toluene-d8, giving kex326 = 1.76 +/- 0.12 s-1, delta H++ = 117.8 +/- 2.1 kJ mol-1, and delta S++ = 120 +/- 7 J K-1 mol-1. An exchange rate constant independent of the concentrations of free phosphine, a strongly positive delta S++, and nearly equal exchange and ligand dissociation rate constants also support a dissociative process. Density functional theory (DFT) calculations for a dissociative process give an estimate for the Pt-P bond energy of 98 kJ mol-1 for R = R' = Me, which is in reasonable agreement with the experimental activation energy given the differences between the substituents used in the calculation and those employed experimentally. DFT calculations on cis-Pt(PR3)2(SiR'3)2 (R = H, CH3; R' = H, CH3) are consistent with the experimental molecular structure and show that methyl substituents on the Si donors are sufficient to induce the observed tetrahedral twist. The optimized Si-Pt-Si angle in cis-Pt(SiH3)2(PH3)2 is not significantly altered by changing the P-Pt-P angle from its equilibrium value of 104 degrees to 80 degrees or 120 degrees. The origin of the tetrahedral twist is therefore not steric but electronic. The Si-Pt-Si angle is consistently less than 90 degrees, but the Si-Si distance is still too long to support an incipient reductive elimination reaction with its attendant Si-Si bonding interaction. Instead, it appears that four tertiary ligands introduce a steric strain which can be decreased by a twist of two of the ligands out of the plane; this twist is only possible when two strong sigma donors are cis to each other, causing a change in the metal's hybridization.     

Pressure dependence of peroxynitrite reactions. Support for a radical mechanism

Activation volumes (delta V++) have been determined for several reactions of peroxynitrite using the stopped-flow technique. Spontaneous decomposition of ONOOH to NO3- in 0.15 M phosphate, pH 4.5, gave delta V++ = 6.0 +/- 0.7 and 14 +/- 1.0 cm3 mol-1 in the presence of 53 microM and 5 mM nitrite ion, respectively. One-electron oxidations of Mo(CN)8(4-) and Fe(CN)6(4-), which are first order in peroxynitrite and zero order in metal complex, gave delta V++ = 10 +/- 1 and 11 +/- 1 cm3 mol-1, respectively, at pH 7.2. The limiting yields of oxidized metal complex were found to decrease from 61 to 30% of the initially added peroxynitrite for Mo(CN)8(3-) and from 78 to 47% for Fe(CN)6(3-) when the pressure was increased from 0.1 to 140 MPa. The bimolecular reaction between CO2 and ONOO- was determined by monitoring the oxidation of Fe(CN)6(4-) by peroxynitrite in bicarbonate-containing 0.15 M phosphate, pH 7.2, for which delta V++ = -22 +/- 4 cm3 mol-1. The Fe(CN)6(3-) yield decreased by approximately 20% upon increasing the pressure from atmospheric to 80 MPa. Oxidation of Ni(cyclam)2+ by peroxynitrite, which is first order in each reactant, was characterized by delta V++ = -7.1 +/- 2 cm3 mol-1, and the thermal activation parameters delta H++ = 4.2 +/- 0.1 kcal mol-1 and delta S++ = -24 +/- 1 cal mol-1 K-1 in 0.15 M phosphate, pH 7.2. These results are discussed within the context of the radical cage hypothesis for peroxynitrite reactivity.     

Kinetics and mechanisms of reactions of methyldioxorhenium(V) in aqueous solutions: dimer formation and oxygen-atom abstraction reactions

The stable compound CH3ReO3 (MTO), upon treatment with aqueous hypophosphorous acid, forms a colorless metastable species designated MDO, CH3ReO2(H2O)n (n = 2). After standing, MDO is first converted to a yellow dimer (lambda max = 348 nm; epsilon = 1.3 x 10(4) L mol-1 cm-1). That reaction follows second-order kinetics with k = 1.4 L mol-1 s-1 in 0.1 M aq trifluoromethane sulfonic acid at 298 K. Kinetics studies as functions of temperature gave delta S++ = -4 +/- 15 J K-1 mol-1 and delta H++ = 71.0 +/- 4.6 kJ mol-1. A much more negative value of delta S++ would be expected for simple dimerization, suggesting the release of one or more molecules of water in forming the transition state. If solutions of the dimer are left for a longer period, an intense blue color results, followed by precipitation of a compound that does, even after a long time, retain the Re-CH3 bond in that aq. hydrogen peroxide generates the independently known CH3Re(O)(O2)2(H2O). The blue compound may be analogous to the intensely colored purple cation [(Cp*Re)3(mu 2-O)3(mu 3-O)3ReO3]+. If a pyridine N-oxide is added to the solution of the dimer, it is rapidly but not instantaneously lost at the same time that a catalytic cycle, separately monitored by NMR, converts the bulk of the PyO to Py according to this stoichiometric equation in which MDO is the active intermediate: C5H5NO + H3PO2-->C5H5N + H3PO3. A thorough kinetic study and the analysis by mathematical and numerical simulations show that the key step is the conversion of the dimer D into a related species D* (presumably one of the two mu-oxo bonds has been broken); the rate constant is 5.6 x 10(-3) s-1. D* then reacts with PyO just as rapidly as MDO does. This scheme is able to account for the kinetics and other results.     

Kinetics and mechanism of complex formation of nickel(II) with tetra-N-alkylated cyclam in N,N-dimethylformamide (DMF): comparative study on the reactivity and solvent exchange of the species Ni(DMF)6(2+) and Ni(DMF)5Cl+

13C NMR was used to study the rate of DMF exchange in the nickel(II) cation Ni(DMF)6(2+) and in the monochloro species Ni(DMF)5Cl+ with 13C-labeled DMF in the temperature range of 193-395 K in DMF (DMF = N,N-dimethylformamide). The kinetic parameters for solvent exchange are kex = (3.7 +/- 0.4) x 10(3) s-1, delta H++ = 59.3 +/- 5 kJ mol-1, and delta S++ = +22.3 +/- 14 J mol-1 K-1 for Ni(DMF)6(2+) and kex = (5.3 +/- 1) x 10(5) s-1, delta H++ = 42.4 +/- 4 kJ mol-1, and delta S++ = +6.7 +/- 15 J mol-1 K-1 for Ni(DMF)5Cl+. Multiwavelength stopped-flow spectrophotometry was used to study the kinetics of complex formation of the cation Ni(DMF)6(2+) and of the 100-fold more labile cation Ni(DMF)5Cl+ with TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and TEC (1,4,8,11-tetraethyl-1,4,8,11-tetraazacyclotetradecane) in DMF at 298 K and I = 0.6 M (tetra-n-butylammoniumperchlorate). Equilibrium constants K for the addition of the nucleophiles DMF, Cl-, and Br- to the complexes Ni(TMC)2+ and Ni(TEC)2+ were determined by spectrophotometric titration. Formation of the complexes Ni(TMC)2+ and Ni(TEC)2+ was found to occur in two stages. In the initial stage, fast, second-order nickel incorporation with rate constants k1(TMC) = 99 +/- 5 M-1 s-1 and k1 (TEC) = 235 +/- 12 M-1 s-1 leads to the intermediates Ni(TMC)int2+ and Ni(TEC)int2+, which have N4-coordinated nickel. In the second stage, these intermediates rearrange slowly to form the stereochemically most stable configuration. First-order rate constants for the one-step rearrangement of Ni(TMC)int2+ and the two-step rearrangment of Ni(TEC)int2+ are presented. Because of the rapid formation of Ni(DMF)5Cl+, the reactions of Ni(DMF)6(2+) with TMC and TEC are accelerated upon the addition of tetra-n-butylammoniumchloride (TBACl) and lead to the complexes Ni(TMC)Cl+ and Ni(TEC)Cl+, respectively. For initial concentrations such that [TBACl]o/[nickel]o > or = 20, intermediate formation is 230 times (TMC) and 47 times (TEC) faster than in the absence of chloride. The mechanism of complex formation is discussed.     

Mechanistic investigation of the oxygen-atom-transfer reactivity of dioxo-molybdenum(VI) complexes

The oxygen-atom-transfer (OAT) reactivity of [LiPrMoO2(OPh)] (1, LiPr=hydrotris(3-isopropylpyrazol-1-yl)borate) with the tertiary phosphines PEt3 and PPh2Me in acetonitrile was investigated. The first step, [LiPrMoO2(OPh)]+PR3-->[LiPrMoO(OPh)(OPR3)], follows a second-order rate law with an associative transition state (PEt3, DeltaH not equal=48.4 (+/-1.9) kJ mol-1, DeltaS not equal=-149.2 (+/-6.4) J mol-1 K-1, DeltaG not equal=92.9 kJ mol-1; PPh2Me, DeltaH not equal=73.4 (+/-3.7) kJ mol-1, DeltaS not equal=-71.9 (+/-2.3) J mol-1 K-1, DeltaG not equal=94.8 kJ mol-1). With PMe3 as a model substrate, the geometry and the free energy of the transition state (TS) for the formation of the phosphine oxide-coordinated intermediate were calculated. The latter, 95 kJ mol-1, is in good agreement with the experimental values. An unexpectedly large O-P-C angle calculated for the TS suggests that there is significant O-nucleophilic attack on the P--C sigma* in addition to the expected nucleophilic attack of the P on the Mo==O pi*. The second step of the reaction, that is, the exchange of the coordinated phosphine oxide with acetonitrile, [LiPrMoO(OPh)(OPR3)]+MeCN-->[LiPrMoO(OPh)(MeCN)]+OPR3, follows a first-order rate law in MeCN. A dissociative interchange (Id) mechanism, with activation parameters of DeltaH not equal=93.5 (+/-0.9) kJ mol-1, DeltaS not equal=18.2 (+/-3.3) J mol-1 K-1, DeltaG not equal=88.1 kJ mol-1 and DeltaH not equal=97.9 (+/-3.4) kJ mol-1, DeltaS not equal=47.3 (+/-11.8) J mol-1 K-1, DeltaG not equal=83.8 kJ mol-1, for [LiPrMoO(OPh)(OPEt3)] (2 a) and [LiPrMoO(OPh)(OPPh2Me)] (2 b), respectively, is consistent with the experimental data. Although gas-phase calculations indicate that the Mo--OPMe3 bond is stronger than the Mo--NCMe bond, solvation provides the driving force for the release of the phosphine oxide and formation of [LiPrMoO(OPh)(MeCN)] (3).     

The first structural characterization and determination of the isomerization activation parameters of a chiral phosphatitanocene

The activation parameters (delta G++298 = 11.5 (+/- 1.0) kcal mol-1, delta H++ = 16.3 (+/- 3.0) kcal mol-1, delta S++ = 16 (+/- 11) cal mol-1 K-1) have been determined for the rac to meso isomerization of a phosphametallocene, bis(3,4-dimethyl-2-phenylphospholyl)titanium dichloride, 2, which has been structurally characterized.     

Thermochemistry of methyl and ethyl nitro, RNO2, and nitrite, RONO, organic compounds

Computational quantum theory is employed to determine the thermochemical properties of n-alkyl nitro and nitrite compounds: methyl and ethyl nitrites, CH3ONO and C2H5ONO, plus nitromethane and nitroethane, CH3NO2 and C2H5NO2, at 298.15 K using multilevel G3, CBS-QB3, and CBS-APNO composite methods employing both atomization and isodesmic reaction analysis. Structures and enthalpies of the corresponding aci-tautomers are also determined. The enthalpies of formation for the most stable conformers of methyl and ethyl nitrites at 298 K are determined to be -15.64 +/- 0.10 kcal mol-1 (-65.44 +/- 0.42 kJ mol-1) and -23.58 +/- 0.12 kcal mol-1 (-98.32 +/- 0.58 kJ mol-1), respectively. DeltafHo(298 K) of nitroalkanes are correspondingly evaluated at -17.67 +/- 0.27 kcal mol-1 (-74.1 +/- 1.12 kJ mol-1) and -25.06 +/- 0.07 kcal mol-1 (-121.2 +/- 0.29 kJ mol-1) for CH3NO2 and C2H5NO2. Enthalpies of formation for the aci-tautomers are calculated as -3.45 +/- 0.44 kcal mol-1 (-14.43 +/- 0.11 kJ mol-1) for aci-nitromethane and -14.25 +/- 0.44 kcal mol-1 (-59.95 +/- 1.84 kJ mol-1) for the aci-nitroethane isomers, respectively. Data are evaluated against experimental and computational values in the literature with recommendations. A set of thermal correction parameters to atomic (H, C, N, O) enthalpies at 0 K is developed, to enable a direct calculation of species enthalpy of formation at 298.15 K, using atomization reaction and computation outputs.     

Energetics of C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols. enthalpies of formation of XCH(2)CH(2)OH (X = F, Cl, Br, I) compounds and of the 2-hydroxyethyl radical

The energetics of the C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-chloro-, 2-bromo-, and 2-iodoethanol, at 298.15 K, were determined as Delta(f)H(degree)m(CH2CH2OH, l) = -315.5 +/- 0.7 kJ.mol-1, Delta(f)H(degree)mBrCH2CH2OH, l) = -275.8 +/- 0.6 kJ.mol-1, Delta(f)H(degree)m(ICH2CH2OH, l) = -207.3 +/- 0.7 kJ.mol-1, by rotating-bomb combustion calorimetry. The corresponding standard molar enthalpies of vaporization, Delta(vap)H(degree)m(ClCH2CH2OH) = 48.32 +/- 0.37 kJ.mol-1, Delta(vap)H(degree)m(BrCH2CH2OH) = 54.08 +/- 0.40 kJ.mol-1, and Delta(vap)H(degree)m(ICH2CH2OH) = 57.03 +/- 0.20 kJ.mol-1 were also obtained by Calvet-drop microcalorimetry. The condensed phase and vaporization enthalpy data lead to Delta(f)H(degree)m(ClCH2CH2OH, g) = -267.2 +/- 0.8 kJ.mol-1, Delta(f)H(degree)m(BrCH2CH2OH, g) = -221.7 +/- 0.7 kJ.mol-1, and Delta(f)H(degree)m(ICH2CH2OH, g) = -150.3 +/- 0.7 kJ.mol-1. These values, together with the enthalpy of selected isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3LYP/cc-pVTZ) and CBS-QB3 calculations were used to derive the enthalpies of formation of gaseous 2-fluoroethanol, Delta(f)H(degree)m(FCH2CH2OH, g) = -423.6 +/- 5.0 kJ.mol-1, and of the 2-hydroxyethyl radical, Delta(f)H(degree)m(CH2CH2OH, g) = -28.7 +/- 8.0 kJ.mol-1. The obtained thermochemical data led to the following carbon-halogen bond dissociation enthalpies: DHo(X-CH2CH2OH) = 474.4 +/- 9.4 kJ.mol-1 (X = F), 359.9 +/- 8.0 kJ.mol-1 (X = Cl), 305.0 +/- 8.0 kJ.mol-1 (X = Br), 228.7 +/- 8.1 kJ.mol-1 (X = I). These values were compared with the corresponding C-X bond dissociation enthalpies in XCH2COOH, XCH3, XC2H5, XCH=CH2, and XC6H5. In view of this comparison the computational methods mentioned above were also used to obtain Delta(f)H(degree)m-594.0 +/- 5.0 kJ.mol-1 from which DHo(F-CH2COOH) = 435.4 +/- 5.4 kJ.mol-1. The order DHo(C-F) > DHo(C-Cl) > DHo(C-Br) > DHo(C-I) is observed for the haloalcohols and all other RX compounds. It is finally concluded that the major qualitative trends exhibited by the C-X bond dissociation enthalpies for the series of compounds studied in this work can be predicted by Pauling's electrostatic-covalent model.     

Insight into binding of alkanes to transition metals from NMR spectroscopy of isomeric pentane and isotopically labeled alkane complexes

Alkane complexes of the type Cp'Re(CO)2(alkane) (Cp' = cyclopentadienyl or (isopropyl)cyclopentadienyl; alkane = isotopomers of n-pentane and cyclopentane) have been characterized using NMR spectroscopy following photolysis of Cp'Re(CO)3 in the appropriate alkane at 163-193 K. In the case of n-pentane, three different complexes are observed corresponding to binding of the three different types of carbon in this alkane. ROESY NMR experiments indicate that these isomeric complexes are slowly interconverting intramolecularly at 173 K. The order of the energetically preferred site of coordination is methylene (C2) approximately central methylene (C3) > methyl (C1) but with a spread of <0.2 kcal mol-1. Isotopic perturbation of resonance (IPR) experiments, conducted on several isotopomers of (i-PrCp)Re(CO)2(1-pentane), showed a large shielding of the 1H NMR chemical shift of the proton in a bound CHD2 moiety (delta -3.62) and CH2D (delta -2.64) compared with that of a bound CH3 moiety (delta -1.99). Likewise, the value of 1JCH for the coordinated methyl group of isotopomers of (i-PrCp)Re(CO)2(1-pentane) reduces in the order CH3 > CH2D > CHD2. This suggests that the alkane coordinates in an eta2-C,H fashion with a rapid exchange of bound hydrogen or deuterium within a methyl or methylene group, and that binding of a hydrogen atom is preferred over a deuterium by an amount of 0.23 +/- 0.03 kcal mol-1.     

Activation parameters for the reactive intermediates relevant to carbonylation catalysts based on cobalt carbonyls

Time-resolved spectroscopic techniques have been used to prepare and to interrogate transient species that are models for reactive intermediates in cobalt-catalyzed hydroformylation. Flash photolysis of acetylcobalt carbonyl complexes of the type RC(O)Co(CO)3(PR'3) (A; R = CH3, CD3, or C2H5; R' = Ph or nBu) leads to CO photodissociation to give the "unsaturated" intermediate [RC(O)Co(CO)2(PR'3)] (I), which decays by two competitive pathways, alkyl migration to the cobalt to give RCo(CO)3PR'3 (M) and reaction with CO to re-form A. With the perdeuterioacetyl complex (R = CD3, R' = Ph), rate constants both of CO trapping (kco) and of methyl migration (kM) were just slightly smaller than those of the perprotio analogue (kh/kd = 1.04 +/- 0.01 and 1.07 +/- 0.09, respectively). Thus, any stabilization of the "vacant" coordination site of I by agostic interactions with the acetyl methyl group appears to be kinetically insignificant, consistent with the previous conclusion (Inorg. Chem. 2000, 39, 3098-3106) that this site is stabilized by an eta 2-coordinated carbonyl. Changing the phosphine ligand has a greater influence on the kinetics of I. The species generated by the flash photolysis of the trialkyl phosphine complex CH3C(O)Co-(CO)3(P(nBu3)) exhibited a much larger kM than was the case for the PPh3 analogue, although there was little difference in the kco values. Similarly, kM proved to be sensitive to the nature of R as demonstrated by the slower alkyl migration (at 298 K) for the intermediate formed by CO photodissociation from the propionyl complex C2H5C(O)Co(CO)3PPh3 relative to the acetyl analogue. Nonetheless, all these intermediates displayed analogous time-resolved infrared spectra and general kinetics behavior in benzene solution (implying common mechanisms for decay), so it is concluded that all are present as the eta 2-chelated acyl structure under these conditions.     

Aggregation and C-N rotation of the lithium salt of N,N-dimethyldiphenylacetamide

[formula: see text] Two methyl 1H NMR signals for the Li salt of N,N-dimethyldiphenylacetamide are observed at low temperature and assigned to the monomer and dimer. From line shape analysis, the dimerization constant (K1,2) is 40 +/- 10 M-1 at 200 K (delta G degree = 1.5 kcal mol-1, delta H degree = 0.8 kcal mol-1, delta S degree = 12 eu) and the activation parameters are delta H++ = 5.5 kcal mol-1 and delta S++ = -18 eu. The C-N bond rotation is too fast to observe on the NMR time scale, indicating a rotation barrier of less than 10 kcal mol-1.     

Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes

The red, five-coordinate complexes Ru(CO)Cl(PPh(3))2(CH=CHPh) and [Ru(CO)Cl(PPh(3))2]2(mu-CH=CHC(6)H(4)CH=CH) undergo reversible coordination of PPh(3) at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh(3))3(CH=CHPh) and [Ru(CO)Cl(PPh(3))3]2(mu-CH=CHC(6)H(4)CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh(3))3 were obtained. 1H and 31P NMR spectra between 20 and -70 degrees C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, DeltaH = -17.5 +/- 2.0 kcal/mol and DeltaS = -57.5 +/- 7.6 eu, were obtained for PPh(3) coordination to the monoruthenium complex, and activation parameters, DeltaH = 20.6 +/- 0.7 kcal/mol and DeltaS = 41.6 +/- 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh(3) was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh(3))2]2(mu-CH=CHCH=CH).     

Reactions of the tetrahedral clusters [MCo(3)(CO)(12)](-) (M = Ru, Fe) with functional mono- and diynes

The tetrahedral cluster [RuCo(3)(CO)(12)](-) reacts with various alkynes, including the new PhCtbd1;CC(O)NHCH(2)Ctbd1;CH (L(1)()), to afford the butterfly clusters [RuCo(3)(CO)(10)(micro(4)-eta(2)-RC(2)R')](-) (1, R = R' = C(O)OMe; 2, R = H, R' = Ph; 3, R = H, R' = MeC=CH(2); 4, R = H, R' = CH(2)OCH(2)Ctbd1;CH; 5, R = H, R' = CH(2)NHC(O)Ctbd1;CPh), in which the ruthenium atom occupies a hinge position and the alkyne is coordinated in a micro(4)-eta(2) fashion. Reaction of the anions 1-3 with [Cu(NCMe)(4)]BF(4) led to selective loss of the 12e fragment Co(CO)(-) to form [RuCo(2)(CO)(9)(micro(3)-eta(2)-RC(2)R')] (6, R = R' = C(O)OMe; 7, R = H, R' = Ph; 8, R = H, R' = MeC=CH(2)). To prepare functionalized RuCo(3) or FeCo(3) clusters that could be subsequently condensed with a silica matrix via the sol-gel method, we reacted [MCo(3)(CO)(12)](-) (M = Ru, Fe) with the alkyne PhCtbd1;CC(O)NH(CH(2))(3)Si(OMe)(3)(L(2)()) and obtained the butterfly clusters [MCo(3)(CO)(10)(micro(4)-eta(2)-PhC(2)C(O)NH(CH(2))(3)Si(OMe)(3))](-) 9 and 10, respectively. Air-stable [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (11) was obtained from 1,4-bis(trimethylsilyl)butadiyne and reacted with [Cu(NCMe)(4)]BF(4) to give [RuCo(2)(CO)(9)(micro(3)-eta(2)-HC(2)Ctbd1;CSiMe(3))] (12), owing to partial ligand proto-desilylation, and not the expected [RuCo(2)(CO)(9)(micro(3)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))]. Reaction of 11 with [NO]BF(4) afforded, in addition to 12, [RuCo(3)(CO)(9)(NO)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))] (13) owing to selective CO substitution on a wing-tip cobalt atom with NO. The thermal reaction of 11 with [AuCl(PPh(3))] led to replacement of a CO on Ru by the PPh(3) originating from [AuCl(PPh(3))] and afforded [RuCo(3)(CO)(9)(PPh(3))(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (14), also obtained directly by reaction of 11 with one equivalent of PPh(3). Proto-desilylation of 11 using TBAF/THF-H(2)O afforded [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CH)](-) (15) which, by Sonogashira coupling with 1,4-diiodobenzene, yielded the dicluster complex [[RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;C)]](2)C(6)H(4)](2)(-) (16). The crystal structures of NEt(4).3a, NEt(4).4a, 6, NEt(4).11b, NEt(4).14, and [N(n-Bu)(4)].15a have been determined by X-ray diffraction. Preliminary results indicate the potential of silica-tethered alkyne mixed-metal clusters, obtained by the sol-gel method, as precursors to bimetallic particles.     

Bimetallo-radical carbon-hydrogen bond activation of methanol and methane

Carbon-hydrogen bond cleavage reactions of CH3OH and CH4 by a dirhodium(II) diporphyrin complex with a m-xylyl tether (.Rh(m-xylyl)Rh.(1)) are reported. Kinetic-mechanistic studies show that the substrate reactions are bimolecular and occur through the use of two Rh(II) centers in the molecular unit of 1. Second-order rate constants (T = 296 K) for the reactions of 1 with methanol (k(CH3OH) = 1.45 x 10-2 M-1 s-1) and methane (k(CH4) = 0.105 M-1 s-1) show a clear kinetic preference for the methane activation process. The methanol and methane reactions with 1 have large kinetic isotope effects (k(CH3OH)/k(CD3OD) = 9.7 +/- 0.8, k(CH4)/k(CD4) = 10.8 +/- 1.0, T = 296 K), consistent with a rate-limiting step of C-H bond homolysis through a linear transition state. Activation parameters for reaction of 1 with methanol (DeltaH = 15.6 +/- 1.0 kcal mol-1; DeltaS = -14 +/- 5 cal K-1 mol-1) and methane (DeltaH = 9.8 +/- 0.5 kcal mol-1; DeltaS = -30 +/- 3 cal K-1 mol-1) are reported.     

Reactivity of the heterometallic clusters [HMCo3(CO)12] and [Et4N][MCo3(CO)12] (M = Fe, Ru) toward phosphine selenides, including selenium transfer. Crystal structures of [HRuCo3(CO)7(mu-CO)3(mu-dppy)], [MCo2(mu3-Se)(CO)7(mu-dppy)], and [RuCo2(mu3-Se)(CO)7(mu-dppm)] [dppy = Ph2(2-C5H4N)P, dppm = Ph2PCH2PPh2

The reactivity of [HMCo3(CO)12] and [Et4N][MCo3(CO)12] (M = Fe, Ru) toward phosphine selenides such as Ph3PSe, Ph2P(Se)CH2PPh2, Ph2(2-C5H4N)PSe, Ph2(2-C4H3S)PSe, and Ph2[(2-C5H4N)(2-C4H2S)]PSe has been studied with the aim to obtain new selenido-carbonyl bimetallic clusters. The reactions of the hydrido clusters give two main classes of products: (i) triangular clusters with a mu3-Se capping ligand of the type [MCo2(mu3-Se)(CO)(9-x)L(y)] resulting from the selenium transfer (x = y = 1, 2, with L = monodentate ligand; x = 2, 4, and y = 1, 2, with L = bidentate ligand) (M = Fe, Ru) and (ii) tetranuclear clusters of the type [HMCo3(CO)12xL(y)] obtained by simple substitution of axial, Co-bound carbonyl groups by the deselenized phosphine ligand. The crystal structures of [HRuCo3(CO)7(mu-CO)3(mu-dppy)] (1), [MCo2(mu3-Se)(CO)7(mu-dppy)] (M = Fe (16) or Ru (2)), and [RuCo2(mu3-Se)(CO)7(mu-dppm)] (12) are reported [dppy = Ph2(2-C5H4N)P, dppm = Ph2PCH2PPh2]. Clusters 2, 12, and 16 are the first examples of trinuclear bimetallic selenido clusters substituted by phosphines. Their core consists of metal triangles capped by a mu3-selenium atom with the bidentate ligand bridging two metals in equatorial positions. The core of cluster 1 consists of a RuCo3 tetrahedron, each Co-Co bond being bridged by a carbonyl group and one further bridged by a dppy ligand. The coordination of dppy in a pseudoaxial position causes the migration of the hydride ligand to the Ru(mu-H)Co edge. In contrast to the reactions of the hydrido clusters, those with the anionic clusters [MCo3(CO)12]- do not lead to Se transfer from phosphorus to the cluster but only to CO substitution by the deselenized phosphine.