Controlling Oxidative Addition and Reductive Elimination at Tin(I) via Hemi-Lability.

We report on the synthesis of a distannyne supported by a pincer ligand bearing pendant amine donors that is capable of reversibly activating E-H bonds at one or both of the tin centres through dissociation of the hemi-labile N-Sn donor/acceptor interactions. This chemistry can be exploited to sequentially (and reversibly) assemble mixed-valence chains of tin atoms of the type ArSn{Sn(Ar)H}n SnAr (n=1, 2). The experimentally observed (decreasing) propensity towards chain growth with increasing chain length can be rationalized both thermodynamically and kinetically by the electron- withdrawing properties of the -Sn(Ar)H- backbone units generated via oxidative addition.

A Series of Crystallographically Characterized Linear and Branched σ-Alkane Complexes of Rhodium: From Propane to 3-Methylpentane.

Using solid-state molecular organometallic (SMOM) techniques, in particular solid/gas single-crystal to single-crystal reactivity, a series of σ-alkane complexes of the general formula [Rh(Cy2PCH2CH2PCy2)(ηn:ηm-alkane)][BArF4] have been prepared (alkane = propane, 2-methylbutane, hexane, 3-methylpentane; ArF = 3,5-(CF3)2C6H3). These new complexes have been characterized using single crystal X-ray diffraction, solid-state NMR spectroscopy and DFT computational techniques and present a variety of Rh(I)···H-C binding motifs at the metal coordination site: 1,2-η2:η2 (2-methylbutane), 1,3-η2:η2 (propane), 2,4-η2:η2 (hexane), and 1,4-η1:η2 (3-methylpentane). For the linear alkanes propane and hexane, some additional Rh(I)···H-C interactions with the geminal C-H bonds are also evident. The stability of these complexes with respect to alkane loss in the solid state varies with the identity of the alkane: from propane that decomposes rapidly at 295 K to 2-methylbutane that is stable and instead undergoes an acceptorless dehydrogenation to form a bound alkene complex. In each case the alkane sits in a binding pocket defined by the {Rh(Cy2PCH2CH2PCy2)}+ fragment and the surrounding array of [BArF4]- anions. For the propane complex, a small alkane binding energy, driven in part by a lack of stabilizing short contacts with the surrounding anions, correlates with the fleeting stability of this species. 2-Methylbutane forms more short contacts within the binding pocket, and as a result the complex is considerably more stable. However, the complex of the larger 3-methylpentane ligand shows lower stability. Empirically, there therefore appears to be an optimal fit between the size and shape of the alkane and overall stability. Such observations are related to guest/host interactions in solution supramolecular chemistry and the holistic role of 1°, 2°, and 3° environments in metalloenzymes.

Intra- and Interchain Interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and Their Effect on One-, Two-, and Three-Dimensional Order.

Mixed-metal cyanides (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN adopt an AuCN-type structure in which metal-cyanide chains pack on a hexagonal lattice with metal atoms arranged in sheets. The interactions between and within the metal-cyanide chains are investigated using density functional theory (DFT) calculations, 13C solid-state NMR (SSNMR), and X-ray pair distribution function (PDF) measurements. Long-range metal and cyanide order is found within the chains: (-Cu-NC-Au-CN-)∞, (-Ag-NC-Au-CN-)∞, and (-Cu-NC-Ag-NC-Au-CN-)∞. Although Bragg diffraction studies establish that there is no long-range order between chains, X-ray PDF results show that there is local order between chains. In (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN, there is a preference for unlike metal atoms occurring as nearest neighbors within the metal sheets. A general mathematical proof shows that the maximum average number of heterometallic nearest-neighbor interactions on a hexagonal lattice with two types of metal atoms is four. Calculated energies of periodic structural models show that those with four unlike nearest neighbors are most favorable. Of these, models in space group Immm give the best fits to the X-ray PDF data out to 8 Å, providing good descriptions of the short- and medium-range structures. This result shows that interactions beyond those of nearest neighbors must be considered when determining the structures of these materials. Such interactions are also important in (Cu1/3Ag1/3Au1/3)CN, leading to the adoption of a structure in Pmm2 containing mixed Cu-Au and Ag-only sheets arranged to maximize the numbers of Cu···Au nearest- and next-nearest-neighbor interactions.

Room Temperature Acceptorless Alkane Dehydrogenation from Molecular σ-Alkane Complexes.

The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or a sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This is complicated by alkanes being such poor ligands, meaning that binding at metal centers prior to C-H activation is disfavored. We demonstrate that by biasing the pre-equilibrium of alkane binding, by using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane σ-complexes, [Rh(Cy2PCH2CH2PCy2)(η:η-(H3C)CH(CH3)2][BArF4] and [Rh(Cy2PCH2CH2PCy2)(η:η-C6H12)][BArF4] can be prepared by simple hydrogenation in a solid/gas single-crystal to single-crystal transformation of precursor alkene complexes. Solid-gas H/D exchange with D2 occurs at all C-H bonds in both alkane complexes, pointing to a variety of low energy fluxional processes that occur for the bound alkane ligands in the solid-state. These are probed by variable temperature solid-state nuclear magnetic resonance experiments and periodic density functional theory (DFT) calculations. These alkane σ-complexes undergo spontaneous acceptorless dehydrogenation at 298 K to reform the corresponding isobutene and cyclohexadiene complexes, by simple application of vacuum or Ar-flow to remove H2. These processes can be followed temporally, and modeled using classical chemical, or Johnson-Mehl-Avrami-Kologoromov, kinetics. When per-deuteration is coupled with dehydrogenation of cyclohexane to cyclohexadiene, this allows for two successive KIEs to be determined [kH/kD = 3.6(5) and 10.8(6)], showing that the rate-determining steps involve C-H activation. Periodic DFT calculations predict overall barriers of 20.6 and 24.4 kcal/mol for the two dehydrogenation steps, in good agreement with the values determined experimentally. The calculations also identify significant C-H bond elongation in both rate-limiting transition states and suggest that the large kH/kD for the second dehydrogenation results from a pre-equilibrium involving C-H oxidative cleavage and a subsequent rate-limiting ß-H transfer step.

Reversible Encapsulation of Xenon and CH2 Cl2 in a Solid-State Molecular Organometallic Framework (Guest@SMOM).

Reversible encapsulation of CH2 Cl2 or Xe in a non-porous solid-state molecular organometallic framework of [Rh(Cy2 PCH2 PCy2 )(NBD)][BArF4 ] occurs in single-crystal to single-crystal transformations. These processes are probed by solid-state NMR spectroscopy, including 129 Xe SSNMR. Non-covalent interactions with the -CF3 groups, and hydrophobic channels formed, of [BArF4 ]- anions are shown to be important, and thus have similarity to the transport of substrates and products to and from the active site in metalloenzymes.

Modulation of σ-Alkane Interactions in [Rh(L2)(alkane)]+ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η2,η2-σ-Alkane Rh(I), η1-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation.

Solid/gas single-crystal to single-crystal (SC-SC) hydrogenation of appropriate diene precursors forms the corresponding σ-alkane complexes [Rh(Cy2P(CH2) nPCy2)(L)][BArF4] ( n = 3, 4) and [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(L)][BArF4] ( n = 5, L = norbornane, NBA; cyclooctane, COA). Their structures, as determined by single-crystal X-ray diffraction, have cations exhibiting Rh···H-C σ-interactions which are modulated by both the chelating ligand and the identity of the alkane, while all sit in an octahedral anion microenvironment. These range from chelating η2,η2 Rh···H-C (e.g., [Rh(Cy2P(CH2) nPCy2)(η2η2-NBA)][BArF4], n = 3 and 4), through to more weakly bound η1 Rh···H-C in which C-H activation of the chelate backbone has also occurred (e.g., [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(η1-COA)][BArF4]) and ultimately to systems where the alkane is not ligated with the metal center, but sits encapsulated in the supporting anion microenvironment, [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4], in which the metal center instead forms two intramolecular agostic η1 Rh···H-C interactions with the phosphine cyclohexyl groups. CH2Cl2 adducts formed by displacement of the η1-alkanes in solution ( n = 5; L = NBA, COA), [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(κ1-ClCH2Cl)][BArF4], are characterized crystallographically. Analyses via periodic DFT, QTAIM, NBO, and NCI calculations, alongside variable temperature solid-state NMR spectroscopy, provide snapshots marking the onset of Rh···alkane interactions along a C-H activation trajectory. These are negligible in [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4]; in [ RhH(Cy2P(CH2)2( CH)(CH2)2PCy2)(η1-COA)][BArF4], σC-H → Rh σ-donation is supported by Rh → σ*C-H "pregostic" donation, and in [Rh(Cy2P(CH2) nPCy2)(η2η2-NBA)][BArF4] ( n = 2-4), σ-donation dominates, supported by classical Rh(dπ) → σ*C-H π-back-donation. Dispersive interactions with the [BArF4]- anions and Cy substituents further stabilize the alkanes within the binding pocket.

Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.

The controlled catalytic functionalization of alkanes via the activation of C-H bonds is a significant challenge. Although C-H activation by transition metal catalysts is often suggested to operate via intermediate σ-alkane complexes, such transient species are difficult to observe due to their instability in solution. This instability may be controlled by use of solid/gas synthetic techniques that enable the isolation of single-crystals of well-defined σ-alkane complexes. Here we show that, using this unique platform, selective alkane C-H activation occurs, as probed by H/D exchange using D2, and that five different isotopomers/isotopologues of the σ-alkane complex result, as characterized by single-crystal neutron diffraction studies for three examples. Low-energy fluxional processes associated with the σ-alkane ligand are identified using variable-temperature X-ray diffraction, solid-state NMR spectroscopy, and periodic DFT calculations. These observations connect σ-alkane complexes with their C-H activated products, and demonstrate that alkane-ligand mobility, and selective C-H activation, are possible when these processes occur in the constrained environment of the solid-state.

A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques.

The pentane σ-complex [Rh{Cy2 P(CH2 CH2 )PCy2 }(η(2) :η(2) -C5 H12 )][BAr(F) 4 ] is synthesized by a solid/gas single-crystal to single-crystal transformation by addition of H2 to a precursor 1,3-pentadiene complex. Characterization by low temperature single-crystal X-ray diffraction (150 K) and SSNMR spectroscopy (158 K) reveals coordination through two Rh⋅⋅⋅H-C interactions in the 2,4-positions of the linear alkane. Periodic DFT calculations and molecular dynamics on the structure in the solid state provide insight into the experimentally observed Rh⋅⋅⋅H-C interaction, the extended environment in the crystal lattice and a temperature-dependent pentane rearrangement implicated by the SSNMR data.

Solid-state synthesis and characterization of σ-alkane complexes, [Rh(L2)(η(2),η(2)-C7H12)][BAr(F)4] (L2 = bidentate chelating phosphine).

The use of solid/gas and single-crystal to single-crystal synthetic routes is reported for the synthesis and characterization of a number of σ-alkane complexes: [Rh(R2P(CH2)nPR2)(η(2),η(2)-C7H12)][BAr(F)4]; R = Cy, n = 2; R = (i)Pr, n = 2,3; Ar = 3,5-C6H3(CF3)2. These norbornane adducts are formed by simple hydrogenation of the corresponding norbornadiene precursor in the solid state. For R = Cy (n = 2), the resulting complex is remarkably stable (months at 298 K), allowing for full characterization using single-crystal X-ray diffraction. The solid-state structure shows no disorder, and the structural metrics can be accurately determined, while the (1)H chemical shifts of the Rh···H-C motif can be determined using solid-state NMR spectroscopy. DFT calculations show that the bonding between the metal fragment and the alkane can be best characterized as a three-center, two-electron interaction, of which σCH → Rh donation is the major component. The other alkane complexes exhibit solid-state (31)P NMR data consistent with their formation, but they are now much less persistent at 298 K and ultimately give the corresponding zwitterions in which [BAr(F)4](-) coordinates and NBA is lost. The solid-state structures, as determined by X-ray crystallography, for all these [BAr(F)4](-) adducts are reported. DFT calculations suggest that the molecular zwitterions within these structures are all significantly more stable than their corresponding σ-alkane cations, suggesting that the solid-state motif has a strong influence on their observed relative stabilities.

Optimising the acid-base ratio of Mg-Al layered double oxides to enhance CO2 capture performance: the critical role of calcination conditions.

The effect of calcination conditions (ramp rate, calcination temperature and time) on the formation of Mg2Al layered double oxides (Mg2Al LDOs) as well as their CO2 capture performance, has been systematically investigated. This study explores novel insights into the intricate relationship between these calcination conditions and the resulting surface characteristics, which play a vital role in CO2 capture efficiency. Notably, it is revealed that a rapid ramp rate (100 °C min-1) significantly increases surface area and hydroxyl concentration, leading to a 69% increase in CO2 capture efficiency compared to slower ramp rate. Conversely, short calcination times (1 h) and fast ramp rates (100 °C min-1) are observed to compromise CO2 adsorption due to the presence of dehydrated LDHs. A critical acid : base ratio of 0.37, achieved from a fast ramp rate (100 °C min-1) at 400 °C for 2 h, was found as a key threshold for optimising surface properties, effectively balancing favourable hydroxyl and less favourable strong acid sites, thereby maximizing CO2 capture performance.

Sterically rigid bismuth pincer complexes; observation of the growing polymer chain in polar monomer polymerisation.

A family of pyridine dipyrrolide bismuth complexes (Mes,PhL)MX (1-6) (M = Bi, X = O-2,6-Me-C6H3 = OXyl (1); M = Sb, X = OXyl (2); M = Bi, X = O-2,6-iPr-C6H3 = ODipp (3), O-2,6-tBu-C6H3 = OArtBu (4), OtBu (5) and OCMe2Et = OAm (6), N(SiMe3)2 = N'' (7) and CH2Ph (8)) have been prepared and investigated as initiators for the ring-opening polymerisation of lactide monomers. Bismuth lactate complexes (Mes,PhL)Bi{OC(H)(Me)C(O)OR} were prepared as models for the propagating species (R = tBu (9), Me (10), iPr (11)). The first insertion of the lactide monomer is rate limiting and the second and subsequent insertions are more rapid (kinit ≪ kLA2 < kprop), leading to a significant induction period. The sterically demanding, rigid pincer ligand affords a well-defined coordination environment at the metal centre and allows for the enchainment of two lactide monomers to be differentiated spectroscopically ((Mes,PhL)Bi{OC(H)(Me)C(O)}4OX (12-X)), with this species also implied to be the true initiator for the regime of propagation with first order kinetics. Well-controlled first order kinetic data for the polymerisation of L-, D-, rac- and meso-lactide are observed.

Separating electrophilicity and Lewis acidity: the synthesis, characterization, and electrochemistry of the electron deficient tris(aryl)boranes B(C6F5)(3-n)(C6Cl5)n (n = 1-3).

A new family of electron-deficient tris(aryl)boranes, B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 1-3), has been synthesized, permitting an investigation into the steric and electronic effects resulting from the gradual replacement of C(6)F(5) with C(6)Cl(5) ligands. B(C(6)F(5))(2)(C(6)Cl(5)) (3) is accessed via C(6)Cl(5)BBr(2), itself prepared from donor-free Zn(C(6)Cl(5))(2) and BBr(3). Reaction of C(6)Cl(5)Li with BCl(3) in a Et(2)O/hexane slurry selectively produced B(C(6)Cl(5))(2)Cl, which undergoes B-Cl exchange with CuC(6)F(5) to afford B(C(6)F(5))(C(6)Cl(5))(2) (5). While 3 forms a complex with H(2)O, which can be rapidly removed under vacuum or in the presence of molecular sieves, B(C(6)Cl(5))(3) (6) is completely stable to refluxing toluene/H(2)O for several days. Compounds 3, 5, and 6 have been structurally characterized using single crystal X-ray diffraction and represent the first structure determinations for compounds featuring B-C(6)Cl(5) bonds; each exhibits a trigonal planar geometry about B, despite having different ligand sets. The spectroscopic characterization using (11)B, (19)F, and (13)C NMR indicates that the boron center becomes more electron-deficient as n increases. Optimized structures of B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) using density functional theory (B3LYP/TZVP) are all fully consistent with the experimental structural data. Computed (11)B shielding constants also replicate the experimental trend almost quantitatively, and the computed natural charges on the boron center increase in the order n = 0 (0.81) < n = 1 (0.89) < n = 2 (1.02) < n = 3 (1.16), supporting the hypothesis that electrophilicity increases concomitantly with substitution of C(6)F(5) for C(6)Cl(5). The direct solution cyclic voltammetry of B(C(6)F(5))(3) has been obtained for the first time and electrochemical measurements upon the entire series B(C(6)F(5))(3-n)(C(6)Cl(5))(n) (n = 0-3) corroborate the spectroscopic data, revealing C(6)Cl(5) to be a more electron-withdrawing group than C(6)F(5), with a ca. +200 mV shift observed in the reduction potential per C(6)F(5) group replaced. Conversely, use of the Guttmann-Beckett and Childs' methods to determine Lewis acidity on B(C(6)F(5))(3), 3, and 5 showed this property to diminish with increasing C(6)Cl(5) content, which is attributed to the steric effects of the bulky C(6)Cl(5) substituents. This conflict is ascribed to the minimal structural reorganization in the radical anions upon reduction during cyclic voltammetric experiments. Reduction of 6 using Na((s)) in THF results in a vivid blue paramagnetic solution of Na(+) [6](•-); the EPR signal of Na(+)[6](•-) is centered at g = 2.002 with a((11)B) 10G. Measurements of the exponential decay of the EPR signal (298 K) reveal [6](•-) to be considerably more stable than its perfluoro analogue.

Structural Analysis of CYP101C1 from Novosphingobium aromaticivorans DSM12444.

CYP101C1 from Novosphingobium aromaticivorans DSM12444 is a homologue of CYP101D1 and CYP101D2 enzymes from the same bacterium and CYP101A1 from Pseudomonas putida. CYP101C1 does not bind camphor but is capable of binding and hydroxylating ionone derivatives including α- and ß-ionone and ß-damascone. The activity of CYP101C1 was highest with ß-damascone (k(cat)=86 s(-1)) but α-ionone oxidation was the most regioselective (98 % at C3). The crystal structures of hexane-2,5-diol- and ß-ionone-bound CYP101C1 have been solved; both have open conformations and the hexanediol-bound form has a clear access channel from the heme to the bulk solvent. The entrance of this channel is blocked when ß-ionone binds to the enzyme. The heme moiety of CYP101C1 is in a significantly different environment compared to the other structurally characterised CYP101 enzymes. The likely ferredoxin binding site on the proximal face of CYP101C1 has a different topology but a similar overall positive charge compared to CYP101D1 and CYP101D2, all of which accept electrons from the ArR/Arx class I electron transfer system.

Dearomatisation of o-xylene by P450BM3 (CYP102A1).

The oxidation of o-xylene by P450(BM3) from Bacillus megaterium yields, in addition to the products formed by microsomal P450s, two metabolites containing an NIH-shifted methyl group, one of which lacks the aromatic character of the substrate. The failure of the epoxide precursor of these two products to rearrange to the more stable 2,7-dimethyloxepin suggests that ring opening is P450-mediated. With m-xylene, the principal metabolite is 2,4-dimethylphenol. The partition between aromatic and benzylic hydroxylation is primarily governed by the steric prescriptions of the active site rather than by C-H bond reactivity. It is also substrate-dependent, o- and m-xylene appearing to bind to the enzyme in different orientations. The product distributions given by variants containing the F87A mutation, which creates additional space in the active site, resemble those reported for microsomal systems.

Reactivity of the latent 12-electron fragment [Rh(PiBu3)2]+ with aryl bromides: aryl-Br and phosphine ligand C-H activation.

Oxidative addition of aryl bromides to 12-electron [Rh(PiBu(3))(2)][BAr(F)(4)] (Ar(F)=3,5-(CF(3))(2)C(6)H(3)) forms a variety of products. With p-tolyl bromides, Rh(III) dimeric complexes result [Rh(PiBu(3))(2)(o/p-MeC(6)H(4))(mu-Br)](2)[BAr(F)(4)](2). Similarly, reaction with p-ClC(6)H(4)Br gives [Rh(PiBu(3))(2)(p-ClC(6)H(4))(mu-Br)](2)[BAr(F)(4)](2). In contrast, the use of o-BrC(6)H(4)Me leads to a product in which toluene has been eliminated and an isobutyl phosphine has undergone C-H activation: [Rh{PiBu(2)(CH(2)CHCH(3)CH(2))}(PiBu(3))(mu-Br)](2)[BAr(F)(4)](2). Trapping experiments with ortho-bromo anisole or ortho-bromo thioanisole indicate that a possible intermediate for this process is a low-coordinate Rh(III) complex that then undergoes C-H activation. The anisole and thioanisole complexes have been isolated and their structures show OMe or SMe interactions with the metal centre alongside supporting agostic interactions, [Rh(PiBu(3))(2)(C(6)H(4)OMe)Br][BAr(F)(4)] (the solid-state structure of the 5-methyl substituted analogue is reported) and [Rh(PiBu(3))(2)(C(6)H(4)SMe)Br][BAr(F)(4)]. The anisole-derived complex proceeds to give [Rh{PiBu(2)(CH(2)CHCH(3)CH(2))}(PiBu(3))(mu-Br)](2)[BAr(F)(4)](2), whereas the thioanisole complex is unreactive. The isolation of [Rh(PiBu(3))(2)(C(6)H(4)OMe)Br][BAr(F)(4)] and its onward reactivity to give the products of C-H activation and aryl elimination suggest that it is implicated on the pathway of a sigma-bond metathesis reaction, a hypothesis strengthened by DFT calculations. Calculations also suggest that C-H bond cleavage through phosphine-assisted deprotonation of a non-agostic bond is also competitive, although the subsequent protonation of the aryl ligand is too high in energy to account for product formation. C-H activation through oxidative addition is also ruled out on the basis of these calculations. These new complexes have been characterised by solution NMR/ESIMS techniques and in the solid-state by X-ray crystallography.

Sr(3)Co(2)O(4.33)h(0.84): an extended transition metal oxide-hydride.

Reaction of the n = 2 Ruddlesden-Popper oxide Sr(3)Co(2)O(5.80) with CaH(2) yields an extended oxide-hydride phase: Sr(3)Co(2)O(4.33)H(0.84). Neutron powder diffraction data reveal the material adopts a body-centered orthorhombic structure (Immm: a = 3.7551(5) Å, b = 3.7048(4) Å, c = 21.480(3) Å) in which the hydride ions are accommodated within disordered CoO(1.16)H(0.46) layers. Low temperature neutron powder diffraction data show no evidence for long-range magnetic order, suggesting the chemical disorder in the anion lattice of the material leads to magnetic frustration.

A cytochrome P450 class I electron transfer system from Novosphingobium aromaticivorans.

Cytochrome P450 (CYP) enzymes of the CYP101 and CYP111 families from Novosphingobium aromaticivorans are heme monooxygenases that catalyze the hydroxylation of a range of terpenoid compounds. CYP101D1 and CYP101D2 oxidized camphor to 5-exo-hydroxycamphor. CYP101B1 and CYP101C1 oxidized beta-ionone to predominantly 3-R-hydroxy-beta-ionone and 4-hydroxy-beta-ionone, respectively. CYP111A2 oxidized linalool to 8-hydroxylinalool. Physiologically, these CYP enzymes could receive electrons from Arx, a [2Fe-2S] ferredoxin equivalent to putidaredoxin from the CYP101A1 system from Pseudomonas putida. A putative ferredoxin reductase (ArR) in the N. aromaticivorans genome, with high amino acid sequence homology to putidaredoxin reductase, has been over-produced in Escherichia coli and found to support substrate oxidation by these CYP enzymes via Arx with both high activity and coupling of product formation to NADH consumption. The ArR/Arx electron-transport chain has been co-expressed with the CYP enzymes in an E. coli host to provide in vivo whole-cell substrate oxidation systems that could produce up to 6.0 g L(-1) of 5-exo-hydroxycamphor at rates of up to 64 microM (gram of cell dry weight)(-1) min(-1). These efficient biocatalytic systems have potential uses in preparative scale whole-cell biotransformations.

Beta-agostic silylamido and silyl-hydrido compounds of molybdenum and tungsten.

Reactions of bis(imido) compounds (RN)(2)Mo(PMe(3))(n) (n = 2, R = (t)Bu; n = 3, R =2,6-dimethylphenyl (Ar') and 2,6-diisopropylphenyl (Ar)) and (RN)(2)W(PMe(3))(3) (R = 2,6-dimethylphenyl and 2,6-diisopropylphenyl) with silanes afford four types of products: the beta-agostic silylamido compounds (RN)(eta(3)-RN-SiR'(2)-H...)MCl(PMe(3))(2) (M = Mo and W), mono(imides) (RN)MCl(2)(PMe(3))(3) (M = Mo and W), silyl hydride bis(imido) derivative (ArN)(2)W(PMe(3))(H)(SiMeCl(2)), and Si-Cl...W bridged product (ArN)(eta(2)-ArN-SiHMeCl-Cl...)WCl(PMe(3))(2). Reactions of molybdenum compounds (RN)(2)Mo(PMe(3))(m) (m = 2 or 3) with mono- and dichlorosilanes HSiCl(n)R'(3-n) (R' = Me, Ph; n = 1,2) afford mainly the agostic compounds (RN)(eta(3)-RN-SiR'(2)-H...)MoCl(PMe(3))(2), accompanied by small amounts of mono(imido) derivatives (RN)MoCl(2)(PMe(3))(3). In contrast, the latter compounds are the only transition metal products in reactions with HSiCl(3), the silicon co-product being the silanimine dimer (RNSiHCl)(2). The reaction of (ArN)(2)W(PMe(3))(3) with HSiCl(2)Me under continuous removal of PMe(3) affords the silyl hydride species (ArN)(2)W(PMe(3))(SiMeCl(2))H, characterized by NMR and X-ray diffraction. This product is stable in the absence of phosphine, but addition of catalytic amounts of PMe(3) causes a fast rearrangement into the Si-Cl...W bridged product (ArN)(eta(2)-ArN-SiHMeCl-Cl...)WCl(PMe(3))(2). The mechanism of silane addition to complexes (RN)(2)Mo(PMe(3))(n) has been elucidated by means of density functional theory calculations of model complexes (MeN)(2)Mo(PMe(3))(n) (n = 1-3). Complex (MeN)(2)Mo(PMe(3))(2) is found to be the most stable form. It undergoes facile silane-to-imido addition reactions that afford silylamido hydride complexes stabilized by additional Si...H interactions. The ease of this addition increases from HSiMe(2)Cl to HSiCl(3), consistent with experimental observations. The most stable final products of silane addition are the agostic complexes (MeN)(eta(3)-MeN-SiR(2)-H...)MoCl(PMe(3))(2) (R(2) = Me(2), MeCl, Cl(2)) and Cl-bridged silylamido complexes (MeN)(eta(2)-MeN-SiRH-Cl...)MoCl(PMe(3))(2) (R = Me or Cl). In the case of HSiMeCl(2) addition the former is the most stable, but for HSiCl(3) addition the latter is the preferred product. In all cases, the isomeric silyl hydride species (MeN)(2)Mo(PMe(3))(H)(SiClR(2)) are less stable by about 6 kcal mol(-1). Silane additions to the imido ligand of the tris(phosphine) (MeN)(2)Mo(PMe(3))(3) afford octahedral silylamido hydride derivatives. The different isomers of these addition products are destabilized relative to (MeN)(2)Mo(PMe(3))(3) only by 7-24 kcal mol(-1) (for the HSiMe(2)Cl additions), but since the starting tris(phosphine) is 14.8 kcal mol(-1) less stable than (MeN)(2)Mo(PMe(3))(2), silane addition to the latter is a more preferred pathway. A double phosphine dissociation pathway via the species (MeN)(2)Mo(PMe(3)) was ruled out because this complex is by 24.7 kcal mol(-1) less stable than (MeN)(2)Mo(PMe(3))(2).

A visible-light photoactivatable di-nuclear PtIV triazolato azido complex.

A novel PtIV triazolato azido complex [3]-[N1,N3] has been synthesised via a strain-promoted double-click reaction (SPDC) between a PtIV azido complex (1) and the Sondheimer diyne (2). Photoactivation of [3]-[N1,N3] with visible light (452 nm) in the presence of 5'-guanosine monophosphate (5'-GMP) produced both PtIV and PtII 5'-GMP species; EPR spectroscopy confirmed the production of both azidyl and hydroxyl radicals. Spin-trapping of photogenerated radicals - particularly hydroxyl radicals - was significantly reduced in the presence of 5'-GMP.

A novel Pt(iv) mono azido mono triazolato complex evolves azidyl radicals following irradiation with visible light.

The platinum(iv) azido complex trans,trans,trans-[PtIV(N3)2(OH)2(py)2] (1) undergoes cycloaddition with 1,4-diphenyl-2-butyne-1,4-dione (2) under mild, catalyst-free conditions, affording a number of mono and bis click products. The major mono click product (3) exists in MeCN as an equilibrium mixture between two species; 3a and 3b rapidly interconvert through nucleophilic attack of the axial Pt-OH group at the adjacent Ph-CO group. The kinetic and thermodynamic parameters for this interconversion have been measured by selective saturation-transfer NMR spectroscopic experiments and are consistent with cyclisation at the Pt centre. Complex 3b was also characterised by X-ray crystallography. Visible light irradiation (440-480 nm) of 3 in d3-MeCN produces azidyl radicals (N3˙), as demonstrated by EPR spin-trapping with DMPO; no generation of hydroxyl radicals was observed. 1H-195Pt HMBC NMR confirmed that the photoproducts were PtIV rather than PtII species, and HPLC was consistent with these being [3-N3]+ species; no facile photoejection of the triazolato ligand was observed, consistent with MS/MS fragmentation of 3. When 3 was irradiated in the presence of 5'-GMP, no 5'-GMP photoproducts were observed, suggesting that complex 3 is likely to exhibit significantly simplified biological activity (release of azidyl radicals but not DNA binding) compared with complex 1.