O-atom transfer biomimetic oxidation of benzoin in the presence of monooxomolybdenum(IV) thiolate complexes

Novel catalytically active monooxomolybdenum(IV) species containing four thiolate ligands obtainable in solution by NaBH₄ reduction of [Mo^vO(SC₆H₅)₄]⁻, [Mo^vO(Z-cys-Val-OMe)₄]⁻, (Z=benzyloxycarbonyl), or [Mo^vO(S₂C₆H₄)₂]⁻ perform the pyridine-N-oxide oxidation of benzoin in N,N-dimethylformamide at 30 °C. The order of catalytic activity is [Mo^vO(Z-cys-Val-OMe)₄]⁻ > [Mo^vO(S₂C₆H₄)₂]⁻ > [Mo^vO(SC₆H₅)₄]⁻ ([benzoin]/[oxidant]/[catalyst]= 20/20/1), while the oxidation by air under the same catalytic conditions gives a different order, [Mo^vO(Z-cys-Val-OMe)₄]⁻> [Mo^vO(SC₆H₅)₄]⁻ >[Mo^vO(S₂C₆H₄)₂]⁻. During the catalytic cycle in the amine-N-oxide oxidation, two intermediate species, [Mo^IVOL₄]²⁻ and [Mo^VIO₂L₄]²⁻, were detected by ¹H NMR, while in the air oxidation an unidentified Mo(VT) species is involved.     

Heterobimetallic dioxomolybdenum(VI) complexes derived from bis(2-hydroxy-1-naphthaldehyde)malonoyldihydrazone: Synthesis and characterization

The heterobimetallic complexes [MMoO₂(L)(H₂O)₂] (where M = Zn²⁺ (1), Cu²⁺ (2), and Co²⁺ (4)) and [{MMoO₃(H₂L)(H₂O)₂}₂] (where M = Ni²⁺ (3) and Mn²⁺ (5)) are synthesized from bis(2-hydroxy-1-naphthaldehyde)malonoyldihydrazone (H₄L) using the monometallic precursor complex [MoO₂(H₂L)]·H₂O in ethanol. The composition of the complexes is established based on the data obtained from the elemental analysis and molecular weight determinations. The structure of the complexes is discussed in the light of data obtained from molar conductance, magnetic moment, electronic, EPR and IR spectroscopic studies.     

Homoleptic tris(dithiolene) and tetrakis(dithiolene) complexes of uranium(IV)

Reaction of UCl4 with 3 or 4 mol equiv of Na2dddt (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) in THF afforded the first example of a tetrakis(dithiolene) metal compound, [Na4(THF)8U(dddt)4](infinity) (1). The red crystals of 1 are composed of infinite zigzag chains in which Na2(micro-THF)3 fragments ensure the linking of Na2(THF)5U(dddt)4 moieties; the uranium atom is in a dodecahedral environment of eight sulfur atoms. Treatment of UCl4 with 3 mol equiv of Na2dddt in pyridine gave a mixture of tris- and tetrakis(dithiolene) compounds. After addition of 18c6 (18-crown-6), only the tris(dithiolene) complex was obtained and crystallized as orange crystals of [Na(18c6)(py)2]2[U(dddt)3].2py (2.2py) in which the isolated [U(dddt)3]2- anion adopts a slightly distorted trigonal prismatic configuration. A few red crystals of the unsolvated complex 2 and the trinuclear anionic compound [Na(18c6)(py)2]3[Na{U(dddt)3}2] (3) were also obtained along with orange crystals of 2.2py. All the tris(dithiolene) compounds exhibit large folding of the dddt ligand and significant interaction between the C=C double bond and the metal center.     

Effect of pressure on proton-coupled electron transfer reactions of seven-coordinate iron complexes in aqueous solutions

For the first time, the effect of pressure on proton-coupled electron-transfer reactions of two selected seven-coordinate FeIII/II(H2L)(H2O)2 systems [where H2L = 2,6-diacetylpyridine-bis(semicarbazone) and 2,6-diacetylpyridine-bis(semioxamazide), respectively] was examined. The acid-base equilibria of the different Fe(III/II) systems were investigated by spectrophotometric, potentiometric, and electrochemical titrations. On the basis of the obtained species distributions, the pH intervals in which the different protonated forms of the two studied systems exist were defined. In different pH ranges, a different number of protons (from 0 to 3 protons per electron) can be transferred during the redox process, which affects the change in the overall charge on the complexes. For all the different protonation forms of the studied complexes, the change in the redox potentials with pressure was measured and the redox reaction volume was obtained by high-pressure cyclic voltammetry. The results show that in the case of proton-coupled electron transfer, the reaction volume for the neutralization of protons contributes to the overall reaction volume. A linear correlation between Deltaz2 (change in the square of the charge) and the overall reaction volume of the complexes upon reduction, DeltaVcomplex0, was found. The average value of the intrinsic volume change for the selected seven-coordinate iron complexes was estimated from the intercept of the plot of DeltaVcomplex0 versus Deltaz2 to be 9.2 +/- 0.7 cm3 mol(-1). For the combined redox and protonation processes, the data are discussed in terms of linear correlations between Deltaz2 and the redox and neutralization reaction volumes reported in the literature.     

Functional analogue reaction systems of the DMSO reductase isoenzyme family: probable mechanism of S-oxide reduction in oxo transfer reactions mediated by bis(dithiolene)-tungsten(IV,VI) complexes

The recent development of structural and functional analogues of the DMSO reductase family of isoenzymes allows mechanistic examination of the minimal oxygen atom transfer paradigm M(IV) + QO M(VI) O + Q with the biological metals M = Mo and W. Systematic variation of the electronic environment at the WIV center of desoxo bis(dithiolene) complexes is enabled by introduction of para-substituted phenyl groups in the equatorial (eq) dithiolene ligand and the axial (ax) phenolate ligand. The compounds [W(CO)2(S2C2(C6H4-p-X)2)2] (54-60%) have been prepared by ligand transfer from [Ni(S2C2(C6H4-p-X)2)2] to [W(CO)3(MeCN)3]. A series of 25 complexes [W(IV)(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- ([X4,X'], X = Br, F, H, Me, OMe; X' = CN, Br, H, Me, NH2; 41-53%) has been obtained by ligand substitution of five dicarbonyl complexes with five phenolate ligands. Linear free energy relationships between E1/2 and Hammett constant p for the electron-transfer series [Ni(S2C2(C6H4-p-X)2)2]0,1-,2- and [W(CO)2(S2C2(C6H4-p-X)2)2]0,1-,2- demonstrate a substituent influence on electron density distribution at the metal center. The reactions [WIV(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4SO [W(VI)O(OC6H4-p-X')(S2C2(C6H4-p-X)2)2]1- + (CH2)4S with constant substrate are second order with large negative activation entropies indicative of an associative transition state. Rate constants at 298 K adhere to the Hammett equations log(k([X4,X']/k[X4,H]) = rho(ax)sigma(p) and log(k[X4,X']/k([H4,X']) = 4rho(eq)sigma(p). Electron-withdrawing groups (EWG) and electron-donating groups (EDG) have opposite effects on the rate such that k(EWG) > k(EDG). The effects of X' on reactivity are found to be approximately 5 times greater than that of X (rho(ax) = 2.1, rho(eq) = 0.44) in the Hammett equation. Using these and other findings, a stepwise oxo transfer reaction pathway is proposed in which an early transition state, of primary W(IV)-O(substrate) bond-making character, is rate-limiting. This is followed by a six-coordinate substrate complex and a second transition state proposed to involve atom and electron transfer leading to the development of the W(VI)=O group. This work is the most detailed mechanistic investigation of oxo transfer mediated by a biological metal.     

Mono-oxo bis(dithiolene) Mo(IV)/W(IV) complexes as building blocks for sulfide bridged Bi- and Tri-nuclear complexes

A new electron precise, six-electron, sulfide-bicapped trinuclear cluster complex [Et4N]4[Mo(IV)3(mu3-S)2(mnt)6] (1) has been synthesized, where each Mo(IV) atom is seven coordinated. Identical reaction conditions yielded a dimeric complex, [PNP]2[W(V)2(mu2-S)2(mnt)4] (2) from the starting W(IV) analogue due to oxidation by sulfur formed by the auto-oxidation of H2S. Two stepwise reversible reductions and no oxidation of 2 as observed by cyclic voltammetry are correlated with the nonbonding nature of the lowest unoccupied molecular orbital and deeply buried highest occupied molecular orbital by theoretical calculations at the density-functional theory level.     

Kinetics and Mechanism of the oxygenation of triphenylphosphine by bis(ethyl-L-cysteinato)dioxomolybdenum(VI)

Summary The kinetics of oxygen-transfer from [MoO₂(Et-L-cys)₂] to PPh₃ and the reaction between [Mo₂O₃(Et-L-cys)₄] and O₂ in benzene solution have been investigated using spectrophotometric techniques between 25 and 40°. The rate laws-d[Mo⁶⁺]/dt = k₁[Mo⁶⁺][PPh₃] with k₁ (at 35°) = 2.95×10^–4dm³mol^–1s^–1 and -d[Mo⁵⁺]/dt = 2k₃[Mo⁵⁺][O₂] with k₃ (at 35°) = 6.3×10^–2 dm³mol^–1s^–1 account for the kinetic data obtained with activation parameters (at 35°) of H = 46 kJ mol^–1, S = –153 JK^–1mol^–1, and H = 50.8 kJ mol^–1, S = –95 JK^–1 mol^–1 respectively.     

Monomeric monooxomolybdenum(VI) complexes of arylazophenolates with one bidentate arylthiol ligand

Reaction of an excess of 2-aminobenzenethiol or thiosalicylic acid (H2T) with cis-[MoO2L] (H2L=tridentate 2,2-dihydroxyarylazo compound) causes elimination of one oxo ligand to give a monomeric monooxomolybdenum(VI) product [MoOL(T)]. These deep red complexes have been characterized by elemental analyses and spectroscopic techniques.     

X-ray spectroscopy of enzyme active site analogues and related molecules: bis(dithiolene)molybdenum(IV) and -tungsten(IV,VI) complexes with variant terminal ligands

The X-ray absorption spectra at the molybdenum and selenium K-edges and the tungsten L2,3-edges are acquired for a set of 14 Mo(IV) and W(IV,VI) bis(dithiolene) complexes related to the active sites of molybdo- and tungstoenzymes. The set includes square pyramidal [MoIVL(S2C2Me2)2]- (L = O2-, R3SiO-, RO-, RS-, RSe-) and [WIV(OR)(S2C2Me2)2]-, distorted trigonal prismatic [MoIV(CO)(SeR)(S2C2Me2)2]- and [WIV(CO)L(S2C2Me2)2]- (L = RS-, RSe-), and distorted octahedral [WVIO(OR)(S2C2Me2)2]-. The dithiolene simulates the pterin-dithiolene cofactor ligand, and L represents a protein ligand. Bond lengths are determined by EXAFS analysis using the GNXAS protocol. Normalized edge spectra, non-phase-shift-corrected Fourier transforms, and EXAFS data and fits are presented. Bond lengths determined by EXAFS and X-ray crystallography agree to < or = 0.02 A as do the M-Se distances determined by both metal and selenium EXAFS. The complexes [MoIV(QR)(S2C2Me2)2]- simulate protein ligation by the DMSO reductase family of enzymes, including DMSO reductase itself (Q = O), dissimilatory nitrate reductase (Q = S), and formate dehydrogenase (Q = Se). Edge shifts of these complexes correlate with the ligand electronegativities. Terminal ligand binding is clearly distinguished in the presence of four Mo-S(dithiolene) interactions. Similarly, five-coordinate [ML(S2C2Me2)2]- and six-coordinate [M(CO)L(S2C2Me2)2]- are distinguishable by edge and EXAFS spectra. This study expands a previous XAS investigation of bis(dithiolene)metal(IV,V,VI) complexes (Musgrave, K. B.; Donahue, J. P.; Lorber, C.; Holm, R. H.; Hedman, B.; Hodgson, K. O. J. Am. Chem. Soc. 1999, 121, 10297) by including a larger inventory of molecules with variant physiologically relevant terminal ligation. The previous and present XAS results should prove useful in characterizing and refining metric features and structures of enzyme sites.     

Desoxo molybdenum(IV) and tungsten(IV) bis(dithiolene) complexes: monomer-dimer interconversion involving reversible thiol bridge formation

Two series of thiol-bridged dimeric desoxo molybdenum(IV) and tungsten(IV) bis(dithiolene) complexes, [Et(4)N](2)[M(IV)(2)(SR)(2)(mnt)(4)] [M = Mo, R = (1) -Ph, (2) -CH(2)Ph, (3) -CH(2)CH(3), (4) -CH(2)CH(2)OH; M = W, R = (1a) -Ph, (2a) -CH(2)Ph, (3a) -CH(2)CH(3), (4a) -CH(2)CH(2)OH] and one monomeric desoxo complex, [Et(4)N](2)[WIV(SPh)(2)(mnt)(2)] (5a) are reported. These complexes are diamagnetic, and crystal structures of each of the complex (except 5a) exhibits a dimeric {M(IV)(2)(SR)(2)} core without any metal-metal bond where each metal atom possesses hexa coordination. The M-SR distance ranges from 2.437 to 2.484 Angstrom in molybdenum complexes and from 2.418 to 2.469 Angstrom in tungsten complexes. These complexes display Mo-S(R)-Mo angles ranging from 92.84 degrees to 96.20 degrees in the case of 1-4 and W-S(R)-W angles ranging from 91.20 degrees to 96.25 degrees in the case of 1a-4a. Interestingly, both the series of Mo(IV) and W(IV) dimeric complexes respond to an unprecedented interconversion between the dimer and the corresponding hexacoordinated monomer upon change of pH. This pH-dependent interconversion establishes the fact that even the pentacoordinated Mo(IV) and W(IV) bis(dithiolene) moieties are forced to dimerize; these can easily be reverted back to the corresponding monomeric complex, reflecting the utility of dithiolene ligand in stabilizing the Mo(IV)/W(IV) moiety in synthesized complexes similar to the active sites present in native proteins.     

A density functional study of oxygen atom transfer reactions between biological oxygen atom donors and molybdenum(IV) bis(dithiolene) complexes

Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me(3)NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)(2)](2-) and [Mo(OCH(3))(mnt)(2)](-) (mnt = maleonitrile-1,2-dithiolate), which may serve as models for mononuclear molybdenum enzymes of the DMSO reductase family. The reaction between [MoO(mnt)(2)](2-) and trimethylamine N-oxide was found to have an activation energy of 72 kJ/mol and proceed via a transition state (TS) with distorted octahedral geometry, where the Me(3)NO is bound through the oxygen to the molybdenum atom and the N-O bond is considerably weakened. The computational modeling of the reactions between dimethyl sulfoxide (DMSO) and [MoO(mnt)(2)](2-) or [Mo(OCH(3))(mnt)(2)](-) indicated that the former is energetically unfavorable while the latter was found to be favorable. The addition of a methyl group to [MoO(mnt)(2)](2-) to form the corresponding des-oxo complex not only lowers the relative energy of the products but also lowers the activation energy. In addition, the reaction with [Mo(OCH(3))(mnt)(2)](-) proceeds via a TS with trigonal prismatic geometry instead of the distorted octahedral TS geometry modeled for the reaction between [MoO(mnt)(2)](2-) and Me(3)NO.     

Pulse radiolysis studies of U(VI) complexes in aqueous media

The rate constants for the reaction between the hydrated electron and dioxouranium(VI) complexes with carbonate IMDA, NTA, oxalate and chloride ion range from 2 to 4 × 10¹⁰ M⁻¹ sec⁻¹. The insensitivity of the reaction rate to formal charge, potential, and number of water molecules in the equatorial coordination sphere of uranium is interpreted in terms of an electron tunneling mechanism for the reaction. Spectroscopic and structural data are cited to provide evidence consistent with such a mechanism.     

Proton-promoted oxygen atom transfer vs proton-coupled electron transfer of a non-heme iron(IV)-oxo complex

Sulfoxidation of thioanisoles by a non-heme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was remarkably enhanced by perchloric acid (70% HClO(4)). The observed second-order rate constant (k(obs)) of sulfoxidation of thioaniosoles by [(N4Py)Fe(IV)(O)](2+) increases linearly with increasing concentration of HClO(4) (70%) in acetonitrile (MeCN)at 298 K. In contrast to sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+), the observed second-order rate constant (k(et)) of electron transfer from one-electron reductants such as [Fe(II)(Me(2)bpy)(3)](2+) (Me(2)bpy = 4,4-dimehtyl-2,2'-bipyridine) to [(N4Py)Fe(IV)(O)](2+) increases with increasing concentration of HClO(4), exhibiting second-order dependence on HClO(4) concentration. This indicates that the proton-coupled electron transfer (PCET) involves two protons associated with electron transfer from [Fe(II)(Me(2)bpy)(3)](2+) to [(N4Py)Fe(IV)(O)](2+) to yield [Fe(III)(Me(2)bpy)(3)](3+) and [(N4Py)Fe(III)(OH(2))](3+). The one-electron reduction potential (E(red)) of [(N4Py)Fe(IV)(O)](2+) in the presence of 10 mM HClO(4) (70%) in MeCN is determined to be 1.43 V vs SCE. A plot of E(red) vs log[HClO(4)] also indicates involvement of two protons in the PCET reduction of [(N4Py)Fe(IV)(O)](2+). The PCET driving force dependence of log k(et) is fitted in light of the Marcus theory of outer-sphere electron transfer to afford the reorganization of PCET (λ = 2.74 eV). The comparison of the k(obs) values of acid-promoted sulfoxidation of thioanisoles by [(N4Py)Fe(IV)(O)](2+) with the k(et) values of PCET from one-electron reductants to [(N4Py)Fe(IV)(O)](2+) at the same PCET driving force reveals that the acid-promoted sulfoxidation proceeds by one-step oxygen atom transfer from [(N4Py)Fe(IV)(O)](2+) to thioanisoles rather than outer-sphere PCET.     

Generation and reactivity of rhodium(IV) complexes in aqueous solutions

At pH = 1 and 25 degrees C, the Fenton-like reactions of Fe(aq)(2+) with hydroperoxorhodium complexes LRh(III)OOH(2+) (L = (H(2)O)(NH(3))(4), k = 30 M(-1) s(-1), and L = L(2) = (H(2)O)(meso-Me(6)-[14]aneN(4)), k = 31 M(-1) s(-1)) generate short-lived, reactive intermediates, believed to be the rhodium(IV) species LRh(IV)O(2+). In the rapid follow-up steps, these transients oxidize Fe(aq)(2+), and the overall reaction has the standard 2:1 [Fe(aq)(2+)]/[LRhOOH(2+)] stoichiometry. Added substrates, such as alcohols, aldehydes, and (NH(3))(4)(H(2)O)RhH(2+), compete with Fe(aq)(2+) for LRh(IV)O(2+), causing the stoichiometry to change to <2:1. Such competition data were used to determine relative reactivities of (NH(3))(4)RhO(2+) toward CH(3)OH (1), CD(3)OH (0.2), C(2)H(5)OH (2.7), 2-C(3)H(7)OH (3.4), 2-C(3)D(7)OH (1.0), CH(2)O (12.5), C(2)H(5)CHO (45), and (NH(3))(4)RhH(2+) (125). The kinetics and products suggest hydrogen atom abstraction for (NH(3))(4)RhO(2+)/alcohol reactions. A short chain reaction observed with C(2)H(5)CHO is consistent with both hydrogen atom and hydride transfer. The rate constant for the reaction between Tl(aq)(III) and L(2)Rh(2+) is 2.25 x 10(5) M(-1) s(-1).     

Synthesis and structures of bis(dithiolene)-tungsten(IV) complexes related to the active sites of tungstoenzymes

Recent protein crystallographic results on tungsten enzymes and primary sequence relationships between certain molybdenum and tungsten enzymes provoke interest in the generalized bis(dithiolene) complexes [WIV(QR)(S2C2R'2)2]1- and [WVIO(QR)(S2C2R'2)2]1- (Q = O, S, Se) as minimal representations of enzyme sites. The existence and stability of W(IV) complexes have been explored by synthesis. Reaction of [W(CO)2(S2C2Me2)2] (1) with PhO- results in complete CO substitution to give [W(OPh)(S2C2Me2)2]1- (2). Reaction of 1 with PhQ- affords the monocarbonyls [W(CO)(QPh)(S2C2Me2)2]1- (Q = S (3), Se (5)). The use of sterically demanding 2,4,6-Pri3C6H2Q- also yields monocarbonyls, [W(CO)(QC6H2-2,4,6-Pri3)(S2C2Me2)2]1- (Q = S (4), Se (6)). The X-ray structures of square pyramidal 2 and trigonal prismatic 3-6 (with unidentate ligands cis) are described. The tendency to substitute one or both carbonyl ligands in 1 in the formation of [MIV(QAr)(S2C2Me2)2]1- and [MIV(CO)(QAr)(SeC2Me2)2]1- with M = Mo and W is related to the M-Q bond length and ligand steric demands. The results demonstrate a stronger binding of CO by W(IV) than Mo(IV), a behavior previously demonstrated by thermodynamic and kinetic features of zerovalent carbonyl complexes. Complexes 3-6 can be reversibly reduced to W(III) at approximately -1.5 V versus SCE. On the basis of the potential for 2(-2.07 V), monocarbonyl ligation stabilizes W(III) by approximately 500 mV. This work is part of a parallel investigation of the chemistry of bis(dithiolene)-molybdenum (Lim, B. S.; Donahue, J. P.; Holm, R. H. Inorg. Chem. 2000, 39, 263) and -tungsten complexes related to enzyme active sites.     

Oxovanadium(IV) and dioxomolybdenum(VI) salen complexes tethered onto amino-functionalized SBA-15 for the epoxidation of cyclooctene

Oxovanadium(IV) and dioxomolybdenum(VI) salen complexes were firstly tethered onto amino-functionalized mesoporous SBA-15 materials by a stepwise procedure and were screened as catalysts for the epoxidation of cyclooctene. The mesoporous structural integrity throughout the tethering procedure, the successful tethering of the organometallic complexes, the loadings of metal ions and organic ligands as well as the catalyst surface constitution and location of active organometallic species on the SBA-15 support were determined by comprehensive characterization techniques such as XRD, N₂ adsorption/desorption, FT-IR, UV–vis spectroscopy, ICP-AES, XPS and TG/DTA. Catalytic properties in the epoxidation of cyclooctene demonstrate that both tethered oxovanadium(IV) and dioxomolybdenum(VI) catalysts were more active than their respective homogeneous analogue, and the tethered oxovanadium(IV) complex showed the best activity (64.3%) with H₂O₂ as the oxidant and CH₃CN as the solvent.     

Ligand effects on metal-oxygen stretching frequencies in dioxomolybdenum(VI) complexes

Summary Several new seven-coordinated dioxomolybdenum(VI) heterochelates, [MoO₂(AA)(BBB)], where AA = bidentate ligand = ethylenediamine, 2-aminoethylpyridine,o-pheny-lenediamine,o-phenanthroline or 2,2-dipyridyl; BBB = tridentate ligand (the Schiff base derived from benzoylhydrazide and salicylaldehyde), have been synthesized and characterized by elemental analysis, molar conductance, molecular weight, i.r. spectra and magnetic susceptibility measurements. The principle of coordination number expansion of a six coordinate homochelate, [MoO₂(H₂O)(BBB)] was used to prepare the complexes, which are nonelectrolytes, monomers and diamagnetic. The i.r. spectral data reveal that they possess acis-MoO₂ structure. The _sym(OMoO) and _asym(OMoO) shifts and the difference between _sym(OMoO) and _asym(OMoO) have been related to an increase in electron density at the molybdenum atom therein.     

Crystal and supramolecular structures of dioxomolybdenum(VI) and dioxotungsten(VI) complexes of dihydroxybenzoic acids

The tetramethylammonium salts (NMe₄)₂[MO₂(2,3-Hdhb)₂]·2H₂O and (NMe₄)₂[MO₂(3,4-Hdhb)₂]·6H₂O (M = Mo, W; Hdhb = monoprotonated form of 2,3- or 3,4-dihydroxybenzoic acid, 2,3-H₃dhb or 3,4-H₃dhb) were prepared and their crystal structures determined. The structure of [Mg(H₂O)₆](NMe₄)₄[MoO₂(3,4-dhb)(3,4-Hdhb)]₂·13H₂O, obtained by the recrystallization of (NMe₄)₂[MoO₂(3,4-Hdhb)₂] in the presence of magnesium ions, is also reported. The supramolecular interactions of the five structures are discussed in detail concerning the hydrogen bonding patterns involving complexes and water molecules of crystallization.     

An expanded set of functional groups in bis(dithiolene)tungsten(IV,VI) complexes related to the active sites of tungstoenzymes, Including WIV-SR and WVI-O(SR)

The active sites of tungstoenzymes have the formulations W(IV,V)L(S(2)pd)(2) and W(VI)LL'(S(2)pd)(2), in which two pyranopterindithiolene cofactor ligands (S(2)pd) are chelated to a tungsten atom. Ligands L and/or L' are not fully defined in any wild-type enzyme. The feasibility of various coordination fragments (functional groups) in potential bis(dithiolene)tungsten site analogues has been examined in previous work by exploratory synthesis. This investigation expands the range of accessible functional groups. The synthetic scheme originates with [W(CO)(2)(S(2)C(2)Me(2))(2)], whose carbonyl groups are labile to substitution. Complexes [W(IV,VI)LL'(S(2)C(2)Me(2))(2)](1-) are described in terms of their functional groups W(IV,VI)LL'. Reaction of the dicarbonyl with formate in acetonitrile/THF affords W(IV)(CO)(eta(1)-HCO(2)) (4) and in Me(2)SO W(VI)O(eta(1)-HCO(2)) (7) by an oxo transfer reaction. Carboxylates yield six-coordinate W(IV)(eta(2)-O(2)CR) (1-3, R = Ph, Me, Bu(t)) with C(2)(v) symmetry. Reaction of 3 (R = Bu(t)) with Me(3)SiSR (R = C(6)H(2)-2,4,6-Pr(i)(3)) gives W(IV)(SR) (5), which undergoes oxo and sulfido atom transfer to form W(VI)O(SR) (8) and W(VI)S(SR) (9), respectively. Attempts to prepare corresponding selenolate complexes, pertinent to the active site of formate dehydrogenase, were unsuccessful, including reactions of W(VI)OCl (10) with RSe(-). Structure proofs of 2-10 were obtained by X-ray structure determinations. Some 26 functional group types in bis(dithiolene)W(IV,V,VI) molecules have now been achieved by synthesis. It remains to be seen which are incorporated in an enzyme site. A number of them (e.g., 5) are directly analogous to molybdoenzyme sites, and may possess corresponding reactivity with biological substrates, as do W(IV)(OR)/W(VI)O(OR) (prepared earlier) in the reduction of N- and S-oxides by atom transfer.