Electrospray mass spectrometry of trans-[Ru(NO)Cl(dpaH)2] (dpaH=2,2′-dipyridylamine) and ‘caged NO’, [RuCl3(NO)(H2O)2]: loss of HCl and NO from positive ions versus NO and Cl from negative ions

The positive ion electrospray mass spectrometry (ESI-MS) of trans-[Ru(NO)Cl)(dpaH)₂]Cl₂ (dpaH=2,2′-dipyridylamine), obtained from the carrier solvent of H₂O–CH₃OH (50:50), revealed 1+ ions of the formulas [Ru^II(NO⁺)Cl(dpaH)(dpa)]⁺ (m/z=508), [Ru^IIICl(dpaH)(dpa⁻)]⁺ (m/z=478), [Ru^II(NO⁺)(dpa)₂]⁺ (m/z=472), [Ru^III(dpa)₂]⁺ (m/z=442), originating from proton dissociation from the parent [Ru^II(NO⁺)Cl(dpaH)₂]²⁺ ion with subsequent loss of NO (17.4% of dissociative events) or loss of HCl (82.6% of dissociative events). Further loss of NO from the m/z=472 fragment yields the m/z=442 fragment. Thus, ionization of the NH moiety of dpaH is a significant factor in controlling the net ionic charge in the gas phase, and allowing preferential dissociation of HCl in the fragmentation processes. With NaCl added, an ion pair, {Na[Ru^II(NO)Cl(dpa)₂]}⁺ (m/z=530; 532), is detectable. All these positive mass peaks that contain Ru carry a signature ‘handprint’ of adjacent m/z peaks due to the isotopic distribution of ¹⁰⁴Ru, ¹⁰²Ru, ¹⁰¹Ru, ⁹⁹Ru, ⁹⁸Ru and ⁹⁶Ru mass centered around ¹⁰¹Ru for each fragment, and have been matched to the theoretical isotopic distribution for each set of peaks centered on the main isotope peak. When the starting complex is allowed to undergo aquation for two weeks in H₂O, loss of the axial Cl⁻ is shown by the approximately 77% attenuation of the [Ru^II(NO⁺)Cl(dpaH)(dpa)]⁺ ion, being replaced by the [Ru^II(NO⁺)(H₂O)(dpa)₂]⁺ (m/z=490) as the most abundant high-mass species. Loss of H₂O is observed to form [Ru^II(NO⁺)(dpa)₂]⁺ (m/z=472). No positive ion mass spectral peaks were observed for RuCl₃(NO)(H₂O)₂, ‘caged NO’. Negative ions were observed by proton dissociation forming [Ru^II(NO)Cl₃(H₂O)(OH)]⁻ in the ionization chamber, detecting the parent 1− ion at m/z=274, followed by the loss of NO as the main dissociative pathway that produces [Ru^IIICl₃(H₂O)(OH)]⁻ (m/z=244). This species undergoes reductive elimination of a chlorine atom, forming [Ru^IICl₂(H₂O)(OH)]⁻ (m/z=208). The ease of the NO dissociation is increased for the negative ions, which should be more able to stabilize a Ru^III product upon NO loss.     

The synthesis and structural characterization of carborane oligomers connected by carbon-carbon and carbon-boron bonds between icosahedra

The reaction of dilithiated o-carborane (closo-1,2-Li₂-1,2-C₂B₁₀H₁₀) with CuCl₂ gives 1,1′-bis(o-carborane) (1), 1,3′-bis(o-carborane) (2) and 1,4′-bis(o-carborane) (3). Compound 2 (C₄B₂₀H₂₂) crystallizes in the monoclinic space group P2₁/n with A = 6.9275(6), B = 9.7655(8), C = 12.356(1) Å, β = 90.028(2)° and Z = 2. The structure was solved by direct methods and refined to R = 0.048 and R_w = 0.074. Compound 3 (C₄B₂₀H₂₂) crystallizes in the orthorhombic space group P2₁2₁2₁ with A = 6.8854(5), B = 12.523(1), C = 19.847(1) Å and Z = 4. The structure was solved by direct methods and refined to R = 0.078 and R_w = 0.091. The coupling reaction of dilithiated m-carborane (closo-1,7-Li₂-1,7-C₂B₁₀H₁₀) with CuCl₂ results in the formation of 1,1′-bis(m-carborane) (4) and tetra(m-carborane) (5).     

Kinetics of ligand substitution in bis(N-alkylsalicylaldiminato)nickel(II) complexes: A search for kinetically-effective aromatic ring stacking

The square-planar bis chelate complexes Ni(R-sal)₂ (= bis(N-alkyl)salicylaldiminato)nickel(II)) with R = (CH₂)₂Ph (I; Ph = phenyl), (CH₂)₃Ph (II), (CH₂)₄Ph (III) and (CH₂)₂(4-hydroxyphenyl) (IV) were prepared and characterized. ComplexesII and III meet the steric requirements for intramolecular aromatic ring stacking. Stopped-flow spectrophotometry was used to study the kinetics of ligand substitution in complexesI–IV by H₂salen (=N,N′-disalicylidene-ethylenediamine) in acetone. For the substitution of the two bidentate ligands in Ni(R-sal)₂ only one step is kinetically observed which follows a second-order rate law, rate =k[H₂salen] [Ni(R-sal)₂], with k = 43.4 (I), 64.0 (II), 87.0 (III) and 49.5 (IV) M⁻¹ s⁻¹ at 298 K. It is found, therefore, that the size of k does not change significantly upon lengthening of the alkane chain in Ni(Ph(CH₂)_nsal)₂ from n = 2 to 4 and that there is no kinetic evidence for intramolecular stacking interactions. The equilibrium constants and thermodynamic parameters for the formation of the bis adductsIII·(py)₂ and III·(MeOH)₂ in acetone are reported.     

One-electron reduction of selenomethionine oxide

Experimental evidence is provided that selenomethionine oxide (MetSeO) is more readily reducible than its sulfur analogue, methionine sulfoxide (MetSO). Pulse radiolysis experiments reveal an efficient reaction of MetSeO with one-electron reductants, such as e^-_aq (k = 1.2 × 10¹⁰M^-1s^-1), CO^·-₂ (k = 5.9 × 10⁸ M^-1s^-1) and (CH₃)₂) C^·OH (k = 3.5 × 10⁷M^-1s^-1), forming an intermediate selenium-nitrogen coupled zwitterionic radical with the positive charge at an intramolecularly formed Se_∴ N 2σ/1σ* three-electron bond, which is characterized by an optical absorption with λ_max at 375 nm, and a half-life of about 70 μs. The same transient is generated upon HO^· radical-induced one-electron oxidation of selenomethionine (MetSe). This radical thus constitutes the redox intermediate between the two oxidation states, MetSeO and MetSe. Time-resolved optical data further indicate sulfur-selenium interactions between the Se_∴ N transient and GSH. The Se_∴ N transient appears to play a key role in the reduction of selenomethionine oxide by glutathione.     

Dinuclear palladium(II) complexes containing two monofunctional [Pd(en)(pyridine)Cl] units bridged by Se or S. Synthesis, characterization, cytotoxicity and kinetic studies of DNA-binding

Two novel dinuclear palladium(II) complexes, {[Pd(en)Cl]₂(bpse)}(NO₃)₂ (1) and {[Pd(en)Cl]₂ (bpsu)}(NO₃)₂ (2), (where en is ethylenediamine; bpse is bis(3-methyl-4-pyridyl) selenide; bpsu is bis(3-methyl-4-pyridyl) sulfide) have been synthesized. The complexes have been characterized by elemental analysis, IR, ¹H NMR, and ¹³C NMR. They have been assayed for antitumor activity in vitro against the mice leukemia L1210 and the human coloadenocarcinoma HCT8 cell lines. The results show that compound 1 has a lower I.D.₅₀ value against the two cancer cell lines as compared to compound 2; the compounds also shows a lower I.D.₅₀ value than cisplatin against the HCT8 cell line, but a higher I.D.₅₀ value than cisplatin against the L1210 cell line. Binding studies indicate that compound 1 possibly interacts with DNA by a nonintercalative mode. Kinetics of binding of the two compounds to DNA are firstly studied using ethidium bromide as a fluorescence probe with stopped-flow spectrophotometer under pseudo-first-order condition. The stronger binding of two steps in the process of the compounds interacting with DNA are observed, and the k_obs and E_a of binding of the two steps (where k_obs is the observed pseudo-first-order rate constant, E_a is the observed energy of activation) are obtained.     

Kinetics and equilibria of Ga(III)---thiocyanate complex formation. Mechanism of ligand substitution reactions of Ga(III) in aqueous solution

The kinetics and equilibria of complex formation by Ga(III) with NCS⁻ in aqueous solution have been measured over a range of acidities and temperatures, the contributing paths to the reaction resolved, and their rate constants and activation parameters determined. The hydrolysis equilibria required to carry out this resolution of kinetic behaviour have also been measured.

Unlike the other reported complexation reactions of Ga(III) in aqueous solution, the separate reaction pathways can be assigned with no ambiguity. At 25 °C and ionic strength 0.5 M, the observed forward rate constant for the complex formation is described by {k₁ + k₂K_1h/[H⁺] + k₃K_1hK_2h/[H⁺]²} M⁻¹ s⁻¹. For these conditions, the first and second successive hydrolysis constants of Ga(H₂O)₆³⁺ are given by pK_1h = 3.69 ± 0.01 and pK_2h = 3.74 ± 0.04. The rate constants corresponding to the reactions of the species Ga(H₂O)₆³⁺, Ga(H₂O)₅(OH)²⁺ and Ga(H₂O)₄(OH)₂⁺ with NCS⁻ are k₁ = 57 ± 4 M^{−1 −1}, k₂ = (1.08 ± 0.01) × 10⁵ M⁻¹ s⁻¹ and k₃ = 3 × 10⁶ M⁻¹ s⁻¹ respectively. The complexation equilibrium quotient [GaNCS²⁺]/([Ga³⁺][NCS⁻]) has been independently determined by spectrophotometric titration to be 20.8 ± 0.3 M⁻¹ at 25 °C and ionic strength 0.5 M.

These kinetic results lead to an interpretation of the data, and a reinterpretation of other data for aquo-Ga(III) complex formation kinetics from the literature which support the assignment of a dissociative interchange mechanism for these reactions rather than the associative activation mode sometimes proposed.     

Kinetics and mechanism of the stoichiometric oxygenation of [Cu(fla)(idpa)]ClO4 [fla=flavonolate, IDPA=3,3′-imino-bis(N,N-dimethylpropylamine)] and the [Cu(fla)(idpa)]ClO4-catalysed oxygenation of flavonol

Oxygenation of [Cu^II(fla)(idpa)]ClO₄ (fla=flavonolate; IDPA=3,3′-iminobis(N,N-dimethylpropylamine)) in dimethylformamide gives [Cu^II(idpa)(O-bs)]ClO₄ (O-bs=O-benzoylsalicylate) and CO. The oxygenolysis of [Cu^II(fla)(idpa)]ClO₄ in DMF was followed by electronic spectroscopy and the rate law −d[{Cu^II(fla)(idpa)}ClO₄]/dt=k_obs[{Cu^II(fla)(idpa)}ClO₄][O₂] was obtained. The rate constant, activation enthalpy and entropy at 373 K are k_obs=6.13±0.16×10⁻³ M⁻¹ s⁻¹, ΔH^‡=64±5 kJ mol⁻¹, ΔS^‡=−120±13 J mol⁻¹ K⁻¹, respectively. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper gives faster oxygenation rates. The complex [Cu^II(fla)(idpa)]ClO₄ has also been found to be a selective catalyst for the oxygenation of flavonol to the corresponding O-benzoylsalicylic acid and CO. The kinetics of the oxygenolysis in DMF was followed by electronic spectroscopy and the following rate law was obtained: −d[flaH]/dt=k_obs[{Cu^II(fla)(idpa)}ClO₄][O₂]. The rate constant, activation enthalpy and entropy at 403 K are k_obs=4.22±0.15×10⁻² M⁻¹ s⁻¹, ΔH^‡=71±6 kJ mol⁻¹, ΔS^‡=−97±15 J mol⁻¹ K⁻¹, respectively.     

Enantioselective cleavage of activated amino acid esters promoted by chiral palladacycles

The ester cleavage of R- and S-isomers N-CBZ-leucine p-nitrophenyl ester intermolecularly catalyzed by R- (a) and S-stereoisomers (b) of the Pd(II) metallacycle [Pd(C₆H₄C^*HMeNMe₂)Cl(py)] (3) follows the rate expression k_obs = k_o + k_cat [3], where the rate constants k_cat equal 25.8 ± 0.4 and 7.6 ± 0.5 dm³ mol⁻¹ s⁻¹ for the S- and R-ester, respectively, in the case of 3a, but are 5.7 ± 0.6 and 26.7 ± 0.5 dm³ mol⁻¹ s⁻¹ for the S- and R-ester, respectively, in the case of 3b (pH 6.23 and 25°C). Thus, the best catalysis occurs when the asymmetric carbons of the leucine ester and Pd(II) complex are R and S, or S and R configured, respectively. Molecular modeling suggests that the stereoselection results from the spatial interaction between the CH₂CHMe₂ radical of the ester and the -methyl group of 3. A hydrophobic/stacking contact between the leaving 4-nitrophenolate and the coordinated pyridine also seems to play a role. Less efficient intramolecular enantioselection was observed for the hydrolysis of N-t-BOC-S-metthionine p-nitrophenyl ester with R- and S-enantiomers of [Pd(C₆H₄C*HMeNMe₂)Cl] coordinated to sulfur.     

C60-fullerenides of ytterbium and lutetium

Cp^#₂Yb (Cp^#=C₅H₄(CH₂)₂NMe₂) has been obtained by reaction of YbI₂(THF)₂ with 2 equiv. of C₅H₄(CH₂CH₂NMe₂)K in THF. The X-ray structure analysis shows a bent structure with intramolecular coordination of both nitrogen atoms to ytterbium. The reaction of C₆₀-fullerene with Cp^#₂Yb leads to the formation of the fullerenide derivative [Cp^#₂Yb]₂C₆₀, which shows an ESR signal in the solid state and in THF solution at room temperature (solid: ΔH = 50 G, G = 1.9992; solution: ΔH = 10 G, G = 2.0001) and a magnetic moment of 3.6 BM. The lutetium fullerenides CpLu(C₆₀)(DME) (3) and Cp^*Lu(C₆₀)(DME)(C₆H₅CH₃) (4), (Cp = η⁵−C₅H₅, Cp^* = η⁵−C₅Me₅), were obtained by reaction of C₆₀ with CpLu(C₁₀H₈) (DME) and Cp^*Lu(C₁₀H₈) (DME) in toluene. Both complexes are paramagnetic (μ_eff = 1.4 and 0.9 BM) and exhibit temperature-dependent ESR signals (293 K: g = 1.992 and 2.0002 respectively).     

Model reactions of a carbonylation catalyst: phosphite induced migratory CO insertion in [MeIr(CO)2I3]

Carbonylation of the anionic iridium(III) methyl complex, [MeIr(CO)₂I₃]⁻ (1) is an important step in the new iridium-based process for acetic acid manufacture. A model study of the migratory insertion reactions of 1 with P-donor ligands is reported. Complex 1 reacts with phosphites to give neutral acetyl complexes, [Ir(COMe)(CO)I₂L₂] (L = P(OPh)₃ (2), P(OMe)₃ (3)). Complex 2 has been isolated and fully characterised from the reaction of Ph₄As[MeIr(CO)₂I₃] with AgBF₄ and P(OPh)₃; comparison of spectroscopic properties suggests an analogous formulation for 3. IR and ³¹P NMR spectroscopy indicate initial formation of unstable isomers of 2 which isomerise to the thermodynamic product with trans phosphite ligands. Kinetic measurements for the reactions of 1 with phosphites in CH₂Cl₂ show first order dependence on [1], only when the reactions are carried out in the presence of excess iodide. The rates exhibit a saturation dependence on [L] and are inhibited by iodide. The reactions are accelerated by addition of alcohols (e.g. 18× enhancement for L = P (OMe)₃ in 1:3 MeOH-CH₂Cl₂). A reaction mechanism is proposed which involves substitution of an iodide ligand by phosphite, prior to migratory CO insertion. The observed rate constants fit well to a rate law derived from this mechanism. Analysis of the kinetic data shows that k₁, the rate constant for iodide dissociation, is independent of L, but is increased by a factor of 18 on adding 25% MeOH to CH₂Cl₂. Activation parameters for the k₁ step are ΔH^≠ = 71 (±3) kJ mol⁻, ΔS^≠ = −81 (±9) J mol⁻¹ K⁻¹ in CH₂Cl₂ and ΔH^≠ = 60(±4) kJ mol⁻¹, ΔS^≠ = −93(± 12) J mol⁻¹ K⁻¹ in 1:3 MeOH-CH₂Cl₂. Solvent assistance of the iodide dissociation step gives the observed rate enhancement in protic solvents. The mechanism is similar to that proposed for the carbonylation of 1.     

Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato)

New mixed metal complexes SrCu₂(O₂CR)₃(bdmap)₃ (R = CF₃ (1a), CH₃ (1b)) and a new dinuclear bismuth complex Bi₂(O₂CCH₃)₄(bdmap)₂(H₂O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF₂ and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi₂O₃ at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm⁻¹. Crystal data for 1a: C₂₇H₅₁N₆O₉F₉Cu₂Sr/THF, monoclinic space group P2₁/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) ų, Z = 2; for 1b: C₂₇H₆₀N₆O₉Cu₂Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) ų, Z = 8; for 2: C₂₂H₄₈O₁₁N₄Bi₂, monoclinic space group P2₁/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) ų, Z = 4.     

The propensity of alkoxide and aryloxide derivatives of tungsten carbonyls to aggregate in solution. Synthesis and X-ray structures of dinuclear, trinuclear and tetranuclear complexes derived from the MeOW(CO)5 anion

The complex [Et₄N][W(CO)₅OMe] (1) has been prepared from the reaction of the photochemically generated W(CO)₅THF adduct and [Et₄N][OH] in methanol. Complex 1 was shown to undergo rapid CO dissociation in THF to quantitatively provide the dimeric dianion, [W(CO)₄OMe]₂²⁻. The resulting THF insoluble salt [Et₄N]₂[W(CO)₄OMe]₂ (2) has been structurally characterized by X-ray crystallography, with the doubly bridging methoxide ligands being in an anti configuration. Complex 2 was found to subsequently react with excess methoxide ligand in a THF slurry to afford the face-sharing octahedron complex [Et₄N]₃[W₂(CO)₆(OMe)₃] (3) which contains three doubly bridging methoxide groups. In the absence of excess methoxide ligand complex 2 cleanly yields the tetrameric complex [Et₄N]₄[W(CO)₃OMe]₄ (4) which has been structurally characterized as a cubane-like arrangement with triply bridging μ³-methoxide groups and W(CO)₃ units. Although complex 3 was not characterized in the solid state, the closely related glycolate derivative [Et₄N]₃[W₂(CO)₆(OCH₂CH₂OH)₃] (5) was synthesized and its structure determined by X-ray crystallography. The trianions of complex 5 are linked in the crystal lattice by strong intermolecular hydrogen bonds. Crystal data for 2: space group P2₁/n, a = 7.696(2), b = 22.019(4), c = 9.714(2) Å, β = 92.22(3)°, Z = 4, R = 6.43%. Crystal data for 4: space group Fddd, a = 12.433(9), b = 24.01(2), c = 39.29(3) Å, Z = 8, R = 8.13%. Crystal data for 5: space group P2₁2₁2₁, a = 11.43(2), b = 12.91(1), c = 29.85(6) Å, Z = 8, R = 8.29%. Finally, the rate of CO ligand dissociation in the closely related aryloxide derivatives [Et₄N][W(CO)₅OR] (R = C₆H₅ and 3,5-F₂C₆H₃) were measured to be 2.15 × 10⁻² and 1.31 × 10⁻³ s⁻¹, respectively, in THF solution at 5°C. Hence, the value of the rate constant of 2.15 × 10⁻² s⁻¹ establishes a lower limit for the first-order rate constant for CO loss in the W(CO)₅OMe⁻ anion, since the methoxide ligand is a better π-donating group than phenoxide.     

Nitrogen atom transfer and redox chemistry of terpyridyl phosphoraniminato complexes of osmium (IV)

Rapid reactions occur between [Os^VI(tpy)(Cl)₂(N)]X (X = PF₆⁻, Cl⁻, tpy = 2,2′:6′,2″-terpyridine) and aryl or alkyl phosphi nes (PPh₃, PPh₂Me, PPhMe₂, PMe₃ and PEt₃) in CH₂Cl₂ or CH₃CN to give [Os^IV(tpy)(Cl)₂(NPPh₃)]⁺ and its analogs. The reaction between trans-[Os^VI(tpy)(Cl)₂(N)]⁺ and PPh₃ in CH₃CN occurs with a 1:1 stoichiometry and a rate law first order in both PPh₃ and Os^VI with k(CH₃CN, 25°C) = 1.36 ± 0.08 × 10⁴ M⁻ s⁻¹. The products are best formulated as paramagnetic d⁴ phosphoraniminato complexes of Os^IV based on a room temperature magnetic moment of 1.8 μ_B for trans-[Os^IV(tpy)(Cl)₂(NPPh₃)](PF₆), contact shifted ¹H NMR spectra and UV-Vis and near-IR spectra. In the crystal structures of trans-[Os^IV(tpy)(Cl)₂( NPPh₃)](PF₆)·CH₃CN (monoclinic, P2₁/n with a = 13.384(5) Å, b = 15.222(7) Å, c = 17.717(6) Å, β = 103.10(3)°, V = 3516(2) ų, Z = 4, R_w = 3.40, R_w = 3.50) and cis-[Os^IV(tpy)(Cl)₂(NPPh₂Me)]-(PF₆)·CH₃CN (monoclinic, P2₁/c, with a = 10.6348(2) Å, b = 15.146(9) ÅA, c = 20.876(6) Å, β = 97.47(1)°, V = 3334(2) ų, Z = 4, R = 4.00, R_w = 4.90), the long Os-N(P) bond lengths (2.093(5) and 2.061(6) Å), acute Os-N-P angles (132.4(3) and 132.2(4)°), and absence of a significant structural trans effect rule out significant Os-N multiple bonding. From cyclic voltammetric measurements, chemically reversible Os^V/IV and Os^IV/III couples occur for trans-[Os^IV(tpy)(Cl)₂(NPPh₃)](PF₆) in CH₃CN at +0.92 V (Os^V/IV) and −0.27 V (Os^IV/III) versus SSCE. Chemical or electrochemical reduction of trans-[Os^IV(tpy)(Cl)₂(NPPh₃)](PF₆) gives isolable trans-Os^III(tpy)(Cl)₂(NPPh₃). One-electron oxidation to Os^V followed by intermolecular disproportionation and PPh₃ group transfer gives [Os^VI(tpy)Cl₂(N)]⁺, [OS^III(tpy)(Cl)₂(CH₃CN)]⁺ and [Ph₃=N=PPh₃]⁺ (PPN⁺). trans-[Os^IV(tpy)(Cl)₂(NPPh₃)](PF₆) undergoes reaction with a second phosphine under reflux to give PPN⁺ derivatives and Os^II(tpy)(Cl)₂(CH₃CN) in CH₃CN or Os^II(tpy)(Cl)₂(PR₃) in CH₂Cl₂. This demonstrates that the Os^VI nitrido complex can undergo a net four-electron change by a combination of atom and group transfers.     

Substitution reaction mechanisms of dihydrido-ruthenium(II) phosphine complexes: hydribe basicity and molecular hydrogen intermediates

Kinetic and activation parameter data for the reactions of cct-Ru(H)₂(CO)₂(PPh₃)₂ (1) (cct = cis, cis, trans) in THF with thiols, CO and PPh₃ to give cct-RuH(SR)(CO)₂(PPh₃)₂, Ru(CO)₃(PPh₃)₂ and Ru(CO)₂(PPh₃)₂, respectively, reveal a common, rate-determining step, the initial dissociation of H₂ from 1; the activated complex probably resembles the corresponding Ru(η²-H₂) species. Reaction of Ru(H)₂(dppm)₂ (2) (as a cis/trans mixture, DPPM = bis(diphenylphosphino)methane) with thiols initially generated cis- and trans- RuH(SR) (dppm)₂ with a rate that depends on both the type and concentration of thiol. The higher basicity of the hydride ligands in 2 (versus 1), which is demonstrated by deuterium exchange with CD₃OD, gives rise in the thiol reaction to an initial protonation step prior to loss of H₂. A species detected in the thiol reaction is possibly [RuH(η²-H₂ (dppm)₂]², the anticipated intermediate for this reaction and for the hydrogen exchange with alcohol. A longer reaction of 2 with PhCH₂SH gives solely cis-Ru(SCH₂Ph)₂(dppm)₂.     

Hydride complexes of platinum(II) containing unsymmetrical di(phosphine) ligands: synthesis, characterization and evidence for pairwise addition of hydrogen based on parahydrogen induced polarization

Unsymmetrical di(phosphine) ligands (dpp)₂Rop (1a, b = bis(diphenylphosphino)-2-alkyl-3-oxapropane (alkyl = methyl and ethyl)) and (dpp)₂oCy (1c = trans-2-diphenylphosphinocyclohexyl diphenylphosphinite) and their Pt(II) dichloride complexes, PtCl₂((dpp)₂mop) (2a), PtCl₂((dpp)₂eop) (2b) and PtCl₂((dpp)₂oCy) (2c), have been synthesized and characterized by NMR spectroscopy. The crystal structures of 2b and 2c show that the geometry about the platinum centers is square planar. In 2b, the metal and di(phosphine) ligand chelate ring are in a chair conformation, whereas in 2c, the chelate ring conformation is a skewed boat. Initial reaction of sodium borohydride with 2a, b, c yields the monohydride monochloride complexes PtHCl((dpp)₂mop) (5a), PtHCl((dpp)₂eop) (5b) and PtHCl((dpp)₂oCy) (5c). At longer reaction times, fluxional dimeric species are obtained, [PtH((dpp)₂mop)]₂ (4a), [PtH((dpp)₂eop)]₂ (4b) and [PtH((dpp)₂oCy)]₂ (4c),and in the case of 4c two different isomers exist. The dihydride complexes PtH₂((dpp)₂mop) (3a), PtH₂((dpp)₂eop) (3b) and PtH₂((dpp)₂oCy) (3c), are prepared by further reaction of NaBH₄ and 2. Hydrogen cycling is facile in the dihydride complexes 3a, b, c, and oxidative addition of H₂ proceeds in a pairwise manner as determined by the observation of parahydrogen induced polarization (PHIP) in the ¹H NMR spectra. The reductive elimination of H₂ is also shown to be concerted by reaction of dihydride complexes with D₂. Crystal data: 2b (C₃₀H₃₂Cl₆OP₂Pt), monoclinic, space group P2₁/c (No. 14), a = 13.7040(1), b = 11.3430(7), c = 21.3880(9) Å, β = 97.923(9)°, V = 3292.9(2) ų and Z = 4; 2c (C₃₀H₃₀Cl₂OP₂Pt), monoclinic, space group P2₁ (No. 4), a = 11.7360(2), b = 8.4311(2), c = 14.2789(2) Å, β = 101.290(1)°, V = 1385.52(4) ų and Z = 2.     

Studies on the kinetics and mechanism of anation reactions of some six-coordinate complexes of chromium(III) in aqueous solution

Rates of stepwise anation of cis-Cr(ox)₂(H₂O₂)⁻ with SCN⁻/N₃⁻, Cr(acac)₂(H₂O)₂⁺ with SCN⁻ and Cr(atda)(H₂O)₂ with SCN⁻ have been investigated in weakly acidic aqueous solutions. Rate constants, k_I and k_II for the two steps in each system, are composite as k_x = k_x⁰+k_x^X[X⁻] (x = I, II; X⁻ = SCN⁻, N₃⁻). These rate constants have been evaluated also as the corresponding ΔH^≠ and ΔS^≠ values. The results obtained and the plausible I_d mechanism seem to suggest Cr---OOC bond dissociation (hence a strongly negative ΔS^≠) generating the transition state in each system with outer-sphere association forming the precursor complex in the X⁻ dependent paths.     

Kinetics and mechanisms of ligand substitution reactions of molybdenum SO2 complexes. Synthesis and X-ray structure of trans-Mo(CO)2 (dmpe) (PPh3) (SO2)

Kinetic results are reported for intramolecular PPh₃ substitution reactions of Mo(CO)₂(η¹-L)(PPh₃)₂(SO₂) to form Mo(CO)₂(η²-L)(PPh₃)(SO₂) (L = DMPE = (Me)₂PC₂H₄P(Me)₂ and dppe=Ph₂PC₂H₄PPh₂) in THF solvent, and for intermolecular SO₂ substitutions in Mo(CO)₃(η²-L)(η²-SO₂) (L = 2,2′-bipyridine, dppe) with phosphorus ligands in CH₂Cl₂ solvent. Activation parameters for intramolecular PPh₃ substitution reactions: ΔH^≠ values are 12.3 kcal/mol for dmpe and 16.7 kcal/mol for dppe; ΔS^≠ values are −30.3 cal/mol K for dmpe and −16.4 cal/mol K for dppe. These results are consistent with an intramolecular associative mechanism. Substitutions of SO₂ in MO(CO)₃(η²-L)(η²-SO₂) complexes proceed by both dissociative and associative mechanisms. The facile associative pathways for the reactions are discussed in terms of the ability of SO₂ to accept a pair of electrons from the metal, with its bonding transformations of η²-SO₂ to η¹-pyramidal SO₂, maintaining a stable 18-e count for the complex in its reaction transition state. The structure of Mo(CO)₂(dmpe)(PPh₃)(SO₂) was determined crystallographically: P2₁/c, A=9.311(1), B = 16.344(2), C = 18.830(2) Å, ß=91.04(1)°, V=2865.1(7) ų, Z=4, R(F)=3.49%.     

The migratory insertion of carbon monoxide in pentamethylcyclopentadienyliridium (III) complexes. Structural effects on reactivity and mechanism for rhodium and iridium systems

The reactions of complex (C₅Me₅)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh₂, PMePh₂, PMe₂Ph) give the products of alkyl migratory insertion (C₅Me₅Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C₅Me₅)Ir(Cl)(CO)(Ph) or the iodide complexes (C₅Me₅)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C₅Me₅)Ir(Cl)(CO)(Me) with PMePh₂ and PMe₂Ph in acetonitrile yields the chloride substitution product [(C₅Me₅)Ir(CO)(L)(Me)]⁺Cl⁻. Kinetic measurements for the reactions of (C₅Me₅)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C₅Me₅)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step (K = 1.5 (CyNC), 7.3 (PHPh₂), 7.1 (PMePh₂) dm³ mol⁻¹ at 323 K) and k₂ for the slow carbon---carbon bond formation (k₂ (10⁵) = 6.9 (CyNC), 1.2 (PHPh₂), 1.0 (PMePh₂) s⁻¹ at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh₂ obtained between 308 and 338 K, are ΔH^≠ = 106±16 kJ mol⁻¹ and ΔS^≠ = − 14±5 J K⁻¹ mol⁻¹. The reaction of 1a with PMePh₂ proceeds at similar rates in tetrahydrofuran (K = 3.7 dm³ mol⁻¹, k₂ (10⁵) = 1.2 s⁻¹, 323 K). The crystal structure of (C₅Me₅)Ir(Cl)(COMe) (PMe₂Ph) has been determined by X-ray diffraction. C₂₀H₂₉ClOPIr: M_r = 544.1, monoclinic, P2₁/n, A = 8.084 (2), B = 9.030(2), C = 28.715 (3) Å, β = 91.41 (3)°, Z = 4, D_c = 1.71 g cm⁻³, V = 2095.5 ų, room temperatyre, Mo K, γ = 0.71069, μ = 65.55 cm⁻¹, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η⁵-C₅Me₅ molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the Ir---P and the Ir---COMe bonds are eclipsed with respect to C(ring)-methyl bonds.     

In Vivo Metabolism of the Vitamin D Analog, 22-Oxacalcitriol: Evidence for Side-chain Truncation and 17-Hydroxylation

After intravenous administration of the vitamin D₃ analog, 22-oxacalcitriol (OCT), to normal rats plasma metabolites were investigated by HPLC, GC-MS and LC-MS. Five side-chain oxidation metabolites, 24R(OH)OCT, 24S(OH)OCT, (25R)-26(OH)OCT, (25S)-26(OH)OCT and 24oxoOCT, were identified by comparison with the corresponding synthetic compounds. These side-chain oxidation metabolites were similar to those of calcitriol [1,25(OH)₂ vitamin D₃] described previously. Besides these five metabolites, two unique side-chain cleavage metabolites, 20S(OH)-hexanor-OCT and 17,20S(OH)₂-hexanor-OCT, were identified as main metabolites in plasma by GC-MS and LC-MS using a specific chemical reaction. Our studies suggest that OCT is extensively metabolized and circulates in blood as a number of metabolites as well as unchanged OCT. This metabolism includes both unique pathways of C₂₃-O₂₂ cleavage and 17-hydroxylation, in addition to the side-chain oxidation metabolites similar to those of 1,25-(OH)₂D₃.     

Kinetics of nucleophilic attack on coordinated organic moieties Part 29. Mechanism of addition of tertiary phosphines and phosphites to the tropylium ring of [M(CO)3(η-C7H7] (M = Cr, Mo, W) cations

Kinetic studies of the addition of a wide range of tertiary phosphines and phosphites to the tropylium ring of the cation [Cr(CO)₃(η⁷-C₇H₇]⁺ (1) reveal the two-term raw, k_obs = k₁[PR₃] + k₋₁. This is consistent with the reversible equilibrium process (i) which is also confirmed from IR and ¹H NMR studies. In the case of the highly basic nucleophiles PBu₃ⁿ and PEt₂Ph, the rate is dominated by the k₁ term and the equilibrium lies far to the right.

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The first-order rate constants k₁, for addition to the tropylium ring decrease markedly down the series PBu₃ⁿ>PEt₂Ph>P(4-MeOC₆H₄)₃>P(4-MeC₆H₄)₃>P(C₆H_{11 3}>PPh₂(4-MeC₆H₄)>PPh₃>P(2-CNC₂H₄)₃>P(OBuⁿ)₃ (overall variation 10⁴). This reactivity order parallels the decreasing electron availability at the phosphorus centres, as confirmed by the linear correlation between log k₁ and the Tolman Σ_χ values for the nucleophiles. Excellent Hammett and Brønsted correlations are also observed for ring addition by a range of P(4-XC₆H₄)₃ nucleophiles. The Brønsted slope, , of 0.7 conirms the major importance of basicity in determining nucleophilicity towards cation 1. Kinetic studies of the related additions of PBu₃ⁿ to the cations [M(CO)₃(η⁷-C₇H₇]⁺ (M = Mo, W) reveal the rate law, Rate = k₁[M][PBu₃ⁿ, and show only a small dependence of k₁ on the nature of metal (Cr>WMo; 2:1.1:1). These data, together with the associated activation parameters, support a mechanism involving direct addition (k₁) of the phosphorus nucleophiles to the tropylium ring, and are inconsistent with initial rate-determining attack at the metal centre.