Hydrogen storage properties and neutron scattering studies of Mg2(dobdc)--a metal-organic framework with open Mg2+ adsorption sites

The hydrogen storage properties of Mg(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework possessing hexagonal one-dimensional channels decorated with unsaturated Mg(2+) coordination sites, have been examined through low- and high-pressure adsorption experiments, infrared spectroscopy, and neutron scattering studies.     

Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture

Selected metal-organic frameworks exhibiting representative properties--high surface area, structural flexibility, or the presence of open metal cation sites--were tested for utility in the separation of CO(2) from H(2) via pressure swing adsorption. Single-component CO(2) and H(2) adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn(4)O(BTB)(2) (MOF-177, BTB(3-) = 1,3,5-benzenetribenzoate), Be(12)(OH)(12)(BTB)(4) (Be-BTB), Co(BDP) (BDP(2-) = 1,4-benzenedipyrazolate), H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (Cu-BTTri, BTTri(3-) = 1,3,5-benzenetristriazolate), and Mg(2)(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H(2)/CO(2) gas mixtures relevant to H(2) purification and precombustion CO(2) capture, respectively. In the former case, the results afford CO(2)/H(2) selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal-organic frameworks with a high concentration of exposed metal cation sites, Mg(2)(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO(2)/H(2) separations.     

Stoichiometric reactivity of dialkylamine boranes with alkaline earth silylamides

Reactions of β-diketiminato group 2 silylamides, [HC{(Me)CN(2,6-(i)Pr(2)C(6)H(3))}(2)M(THF)(n){N(SiMe(3))(2)}] (M = Mg, n = 0; M = Ca, Sr, n = 1), and an equimolar quantity of pyrrolidine borane, (CH(2))(4)NH·BH(3), were found to produce amidoborane derivatives of the form [HC{(Me)CN(2,6-(i)Pr(2)C(6)H(3))}(2)MN(CH(2))(4)·BH(3)]. In reactivity reminiscent of analogous reactions performed with dimethylamine borane, addition of a second equivalent of (CH(2))(4)NH·BH(3) to the Mg derivative induced the formation of a species, [HC{(Me)CN(2,6-(i)Pr(2)C(6)H(3))}(2)Mg{N(CH(2))(4) BH(2)NMe(2)BH(3)}], containing an anion in which two molecules of the amine borane substrate have been coupled together through the elimination of one molecule of H(2). Both this species and a calcium amidoborane derivative have been characterised by X-ray diffraction techniques and the coupled species is proposed as a key intermediate in catalytic amine borane dehydrocoupling, in reactivity dictated by the charge density of the group 2 centre involved. On the basis of further stoichiometric reactions of the homoleptic group 2 silylamides, [M{N(SiMe(3))(2)}(2)] (M = Mg, Ca, Sr, Ba), with (CH(3))(2)NH·BH(3) and (i)Pr(2)NH·BH(3) reactivity consistent with successive amidoborane β-hydride elimination and [R(2)N[double bond, length as m-dash]BH(2)] insertion is described as a means to induce the B-N dehydrocoupling between amine borane substrates.     

Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites

The air-free reaction between FeCl(2) and H(4)dobdc (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe(2)(dobdc)·4DMF, a metal-organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer-Emmett-Teller (BET) surface area of 1360 m(2)/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe(II) centers. Gas adsorption isotherms at 298 K indicate that Fe(2)(dobdc) binds O(2) preferentially over N(2), with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O(2) molecule per two iron centers. Remarkably, at 211 K, O(2) uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O(2) molecule per iron center. Mo?ssbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O(2) at low temperature and complete charge transfer to form iron(III) and O(2)(2-) at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O(2) bound to iron in a symmetric side-on mode with d(O-O) = 1.25(1) ? at low temperature and in a slipped side-on mode with d(O-O) = 1.6(1) ? when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe(2)(dobdc) to be a promising material for the separation of O(2) from air at temperatures well above those currently employed in industrial settings.     

Properties of passivation film on carbon electrode in LiPF6/EC+DEC electrolytes

The co-solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) was used to investigate the decomposition of electrolyte in Li-ion batteries. The electrolyte solutions were prepared by mixing in various volume ratios from pure DEC to 7:3 (EC:DEC). The potentials at which they are decomposed on the anodic electrode were examined using cyclic voltammetry. It was found that some kinds of reduction reactions proceeded and a film on the surface of the anode was formed. The film showed different properties, which were dependent on the mixing ratio of the solvents. From our results, we concluded that the best composition ratio of EC:DEC in 1 M LiPF₆/(EC+DEC) system was approximately 4:6 (EC:DEC, volume ratio).     

Catalytic enantioselective allylation of ketoimines

A general catalytic allylation of simple ketoimines was developed using 1 mol % of CuF.3PPh(3) as catalyst, 1.5 mol % of La(O(i)Pr)(3) as the cocatalyst, and stable and nontoxic allylboronic acid pinacol ester as the nucleophile. This reaction constituted a good template for developing the first catalytic enantioselective allylation of ketoimines. In this case, using LiO(i)Pr as the cocatalyst produced higher enantioselectivity and reactivity than La(O(i)Pr)(3). Thus, using the CuF-cyclopentyl-DuPHOS complex (10 mol %) and LiO(i)Pr (30 mol %) in the presence of (t)BuOH (1 equiv) produced high enantioselectivity up to 93% ee from a range of aromatic ketoimines. Mechanistic studies indicated that LiO(i)Pr accelerates the reaction by increasing the concentration of an active nucleophile, allylcopper.     

Synthesis and molecular structure of piperazidine-bridged bis(phenolate) samarium(II) complex and its reactivity to carbodiimides

The reaction of Sm[N(TMS)(2)](2)(THF)(2) with H(2)L (L = 1,4-bis(2-hydroxy-3-tert-butyl-5-methyl-benzyl)-piperazidine) afforded [SmL(HMPA)(2)](4)·8THF 2 upon treatment with 2 equivalents of HMPA (hexamethyl phosphoric triamide). X-ray crystallographic analysis of 2 reveals a tetrametallic macrocyclic structure, which represents the first example of a crystal structure of a Sm(II) complex stabilized by heteroatom bridged bis(phenolate) ligands. Reduction of carbodiimides RNCNR (R = (i)Pr and Cy) by [SmL](2)(THF) 1, which was formed in situ by the reaction of Sm[N(TMS)(2)](2)(THF)(2) with H(2)L in THF, yielded the Sm(III) complex with an oxalamidinate ligand [LSm{(N(i)Pr)(2)CC(N(i)Pr)(2)}SmL]·THF 3 for (i)PrNCN(i)Pr and the Sm(III) complex with a diamidocarbene ligand [LSm(μ-CyNCNCy)SmL]·5.5THF 4 for CyNCNCy.     

Reactions of an osmium-hexahydride complex with Cytosine, deoxycytidine, and cytidine: the importance of the minor tautomers

Complex OsH(6)(P(i)Pr(3))(2) (1) deprotonates cytosine to give molecular hydrogen and the d(4)-trihydride derivative OsH(3)(cytosinate)(P(i)Pr(3))(2) (2), which in solution exists as a mixture of isomers containing κ(2)-N1,O (2a) and κ(2)-N3,O (2b) amino-oxo and κ(2)-N3,N4 (2c) imino-oxo tautomers. The major isomer 2b associates with the minor one 2c through N-H···N and N-H···O hydrogen bonds to form [2b·2c](2) dimers, which crystallize from saturated pentane solutions of 2. Complex 1 is also able to perform the double deprotonation of cytosine (cytosinate') to afford the dinuclear derivative (P(i)Pr(3))(2)H(3)Os(cytosinate')OsH(3)(P(i)Pr(3))(2) (3), where the anion is coordinated κ(2)-N1,O and κ(2)-N3,N4 to two different OsH(3)(P(i)Pr(3))(2) metal fragments. The deprotonation of deoxycytidine and cytidine leads to OsH(3)(deoxycytidinate)(P(i)Pr(3))(2) (4) and OsH(3)(cytidinate)(P(i)Pr(3))(2) (5), respectively, containing the anion κ(2)-N3,N4 coordinated. Dimer [2b·2c](2) and dinuclear complex 3 have been characterized by X-ray diffraction analysis.     

Synthesis and structural characterization of alkaline-earth-metal bis(amido)silane and lithium oxobis(aminolato)silane complexes

Several of alkaline-earth-metal complexes [(η(2):η(2):μ(N):μ(N)-Li)(+)](2)[{η(2)-Me(2)Si(DippN)(2)}(2)Mg](2-) (4), [η(2)(N,N)-Me(2)Si(DippN)(2)Ca·3THF] (5), [η(2)(N,N)-Me(2)Si(DippN)(2)Sr·THF] (6), and [η(2)(N,N)-Me(2)Si(DippN)(2)Ba·4THF] (7) of a bulky bis(amido)silane ligand were readily prepared by the metathesis reaction of alkali-metal bis(amido)silane [Me(2)Si(DippNLi)(2)] (Dipp = 2,6-i-Pr(2)C(6)H(3)) and alkaline-earth-metal halides MX(2) (M = Mg, X = Br; M = Ca, Sr, Ba, X = I). Alternatively, compounds 5-7 were synthesized either by transamination of M[N(SiMe(3))(2)](2)·2THF (M = Ca, Sr, Ba) and [Me(2)Si(DippNH)(2)] or by transmetalation of Sn[N(SiMe(3))(2)](2), [Me(2)Si(DippNH)(2)], and metallic calcium, strontium, and barium in situ. The metathesis reaction of dilithium bis(amido)silane [Me(2)Si(DippNLi)(2)] and magnesium bromide in the presence of oxygen afforded, however, an unusual lithium oxo polyhedral complex {[(DippN(Me(2)Si)(2))(μ-O)(Me(2)Si)](2)(μ-Br)(2)[(μ(3)-Li)·THF](4)(μ(4)-O)(4)(μ(3)-Li)(2)} (8) with a square-basket-shaped core Li(6)Br(2)O(4) bearing a bis(aminolato)silane ligand. All complexes were characterized using (1)H, (13)C, and (7)Li NMR and IR spectroscopy, in addition to X-ray crystallography.     

FT-IR studies on interactions among components in hexanoyl chitosan-based polymer electrolytes

Fourier transform infrared (FT-IR) spectroscopic studies have been undertaken to investigate the interactions among components in a system of hexanoyl chitosan-lithium trifluoromethanesulfonate (LiCF(3)SO(3))-diethyl carbonate (DEC)/ethylene carbonate (EC). LiCF(3)SO(3) interacts with the hexanoyl chitosan to form a hexanoyl chitosan-salt complex that results in the shifting of the N(COR)(2), CONHR and OCOR bands to lower wavenumbers. Interactions between EC and DEC with LiCF(3)SO(3) has been noted and discussed. Evidence of interaction between EC and DEC has been obtained experimentally. Studies on polymer-plasticizer spectra suggested that there is no interaction between the polymer host and plasticizers. Competition between plasticizer and polymer on associating with Li(+) ions was observed from the spectral data for gel polymer electrolytes. The obtained spectroscopic data has been correlated with the conductivity performance of hexanoyl chitosan-based polymer electrolytes.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

New crystalline aluminum alkoxide oxide fluorides: evidence of the mechanism of the fluorolytic sol-gel reaction

This study reports three new crystalline aluminum isopropoxide oxide fluorides with molar ratios of Al:F equal to 1:1 and 1:1.25. These are the first three representatives isolated without the incorporation of external donor molecules. Compound 1 Al(4)F(4)(μ(4)-O)(μ-O(i)Pr)(5)[H(O(i)Pr)(2)] contains a tetranuclear unit consisting of two different five fold coordinated AlFO(4)-units, with F exclusively in the terminal position. Compound 2, Al(4)F(4)(μ(4)-O)(μ-O(i)Pr)(5)[H(O(i)Pr)(2)]·Al(5)F(5)(μ(5)-O)(μ-O(i)Pr)(8), contains both a tetranuclear unit (as in 1) and a pentanuclear Al-unit. Al-atoms in the latter are five- and six fold coordinated. Compound 3, Al(16)F(20)(μ(4)-O)(4)(μ-O(i)Pr)(20)·2((i)PrOH), exhibits a slightly higher fluorination degree and contains an oligomeric chain of four F-linked tetranuclear Al-units. In addition to X-ray structure analysis, compound 1 was characterized by different solid state MAS NMR techniques, including (27)Al triple quantum MAS NMR and (1)H, (1)H→(13)C CP, (19)F and (27)Al MAS NMR. On the basis of the collected data, a reliable decomposition of (27)Al single pulse MAS NMR spectra and an unambiguous assignment of the resonances to the respective structural AlFO(4)-units are given. The new crystalline aluminum isopropoxide oxide fluorides are direct evidence of the fluorolytic sol-gel mechanism previously discussed.     

Metal-free and dicopper(II) complexes of Schiff base [2 + 2] macrocycles derived from 2,2'-iminobisbenzaldehyde: syntheses, structures, and electrochemistry

Three new bis-terdentate Schiff base [2 + 2] macrocycles (H(2)L(Et), H(2)L(Pr), and H(2)L(Bu)) have been prepared in high yields by 1:1 condensation of 2,2'-iminobisbenzaldehyde with 1,2-diaminoethane, 1,3-diaminopropane, and 1,4-diaminobutane, respectively. Metalation of these macrocycles yields the corresponding dicopper(II) acetate (1, 2, and 3) and tetrafluoroborate (4, 5, and 6) complexes. The structures of H(2)L(Et), H(2)L(Pr), H(2)L(Bu), [Cu(II)(2)L(i)(OAc)(2)]·solvents (where i is Et, Pr or Bu) and [Cu(II)(2)L(Pr)(DMF)(4)] (BF(4))(2)·0.5H(2)O are reported. Intramolecular hydrogen bonding is a feature of the metal-free macrocycles. The copper(II) centers in [Cu(II)(2)L(i)(OAc)(2)]·solvents are four coordinate, and the macrocycles have U-shaped (Et, Bu) or stepped (Pr) conformations. Complex 5 crystallizes with two dimethylformamide (DMF) molecules bound per five coordinate copper(II) center. Electrochemical studies revealed ligand based oxidations for all of the macrocycles and complexes. Complexes 1 and 2 undergo two quasi-reversible oxidations in DCM which are associated with the deposition of a visible film on the electrode after multiple scans in this oxidative region, suggestive of electropolymerization. Complexes 4-6, studied in MeCN, have Cu(II) → Cu(I) redox potentials at more positive potentials than for 1-3.     

Formation and reactivity of the cyclometallated N-heterocyclic carbene complexes [Ru(NHC)'(dppe)(CO)H

Thermolysis of [Ru(PPh(3))(dppe)(CO)HCl] (dppe = 1,2-bis(diphenylphosphino)ethane) with the N-heterocyclic carbenes I(i)Pr(2)Me(2) (1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene), IEt(2)Me(2) (1,3-diethyl-4,5-dimethyl-imidazol-2-ylidene) or ICy (1,3-dicyclohexylimidazol-2-ylidene) gave the cyclometallated carbene complexes [Ru(NHC)'(dppe)(CO)H] (NHC = I(i)Pr(2)Me(2), 4; IEt(2)Me(2), 5; ICy, 6). Dissolution of 4 in CH(2)Cl(2) or CHCl(3) gave the trans-Cl-Ru-P complex [Ru(I(i)Pr(2)Me(2))'(dppe)(CO)Cl] (7), which converted over hours at room temperature to the trans-Cl-Ru-CO isomer 7'. Chloride abstraction from 7 by NaBPh(4) under an atmosphere of H(2) produced the cationic mono-hydride complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)H][BPh(4)] (9), which could also be formed by protonating 4 with 1 eq HBF(4)·OEt(2). Treatment of 4 with excess HBF(4)·OEt(2) followed by extraction into MeCN produced the dicationic acetonitrile complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)(NCMe)(2)][BF(4)](2) (10). The structures of 6, 7, 7' and 10 have been determined by X-ray crystallography.     

Influences on the rotated structure of diiron dithiolate complexes: electronic asymmetry vs. secondary coordination sphere interaction

In the pursuit of a "rotated" structure, and exploration of the influence of the aza nitrogen lone pair, the Fe(I)Fe(I) model complexes wherein two Fe(CO)(3-x)P(x) moieties are significantly twisted from the ideal configuration (torsion angle >30°) are reported. [Fe(2)(μ-S(CH(2))(2)N(i)Pr(X)(CH(2))(2)S)(CO)(4)(κ(2)-dppe)](2)(2+) (X = H, 4; Me, 5) prepared from protonation and methylation, respectively, of [Fe(2)(μ-S(CH(2))(2)N(i)Pr(CH(2))(2)S)(CO)(4)(κ(2)-dppe)](2), 1, possess Φ angles of 34.1 and 35.4° (av.), respectively. Such dramatic twist is attributed to asymmetric substitution within the Fe(2) unit in which a dppe ligand is coordinated to one Fe site in the κ(2)-mode. In the presence of the N···C(CO(ap)) interaction, the torsion angle is decreased to 10.8°, suggesting availability of lone pairs of the aza nitrogen sites within 1 is in control of the twist. Backbones of the bridging diphosphine ligands also affect distortion. For a shorter ligand, the more compact structure of [Fe(2)(μ-S(CH(2))(2)N(i)Pr(CH(2))(2)S)(μ-dppm)(CO)(4)](2), 7, is formed. Dppm in a bridging manner allows achievement of the nearly eclipsed configuration. In contrast, dppe in [Fe(2)(μ-S(CH(2))(2)N(i)Pr(CH(2))(2)S)(μ-dppe)(CO)(4)](2), 6, could twist the Fe(CO)(3-x)L(x) fragment to adopt the least strained structure. In addition, the NC(CO(ap)) interaction would direct the twist towards a specific direction for the closer contact. In return, the shorter N···C(CO(ap)) distance of 3.721(7) ? and larger Φ angle of 26.5° are obtained in 6. For comparison, 3.987(7) ? and 3.9° of the corresponding parameters are observed in 7. Conversion of (μ-dppe)[Fe(2)(μ-S(CH(2))(2)N(i)Pr(CH(2))(2)S)(CO)(5)](2), 2, to complex 1 via an associative mechanism is studied.     

Large effects of ion pairing and protonic-hydridic bonding on the stereochemistry and basicity of crown-, azacrown-, and cryptand-222-potassium salts of anionic tetrahydride complexes of iridium(III)

The compounds [K(Q)][IrH(4)(PR(3))(2)] (Q = 18-crown-6, R = Ph, (i)Pr, Cy; Q = aza-18-crown-6, R = (i)Pr; Q = 1,10-diaza-18-crown-6, R = Ph, (i)Pr, Cy; Q = cryptand-222, R = (i)Pr, Cy) were formed in the reactions of IrH(5)(PR(3))(2) with KH and Q. In solution, the stereochemistry of the salts of [IrH(4)(PR(3))(2)](-) is surprisingly sensitive to the countercation: either trans as the potassium cryptand-222 salts (R = Cy, (i)Pr) or exclusively cis (R = Cy, Ph) as the crown- and azacrown-potassium salts or a mixture of cis and trans (R = (i)Pr). There is IR evidence for protonic-hydridic bonding between the NH of the aza salts and the iridium hydride in solution. In single crystals of [K(18-crown-6)][cis-IrH(4)(PR(3))(2)] (R = Ph, (i)Pr) and [K(aza-18-crown-6)][cis-IrH(4)(P(i)Pr(3))(2)], the potassium bonds to three hydrides on a face of the iridium octahedron according to X-ray diffraction studies. Significantly, [K(1,10-diaza-18-crown-6)][trans-IrH(4)(P(i)Pr(3))(2)] crystallizes in a chain structure held together by protonic-hydridic bonds. In [K(1,10-diaza-18-crown-6)][cis-IrH(4)(PPh(3))(2)], the potassium bonds to two hydrides so that one NH can form an intra-ion-pair protonic-hydridic hydrogen bond while the other forms an inter-ion-pair NH.HIr hydrogen bond to form chains through the lattice. Thus, there is a competition between the potassium and NH groups in forming bonds with the hydrides on iridium. The more basic P(i)R(3) complex has the lower N-H stretch in the IR spectrum because of stronger N[bond]H...HIr hydrogen bonding. The trans complexes have very low Ir-H wavenumbers (1670-1680) due to the trans hydride ligands. The [K(cryptand)](+) salt of [trans-IrH(4)(P(i)Pr(3))(2)](-) reacts with WH(6)(PMe(2)Ph)(3) (pK(alpha)(THF) 42) to give an equilibrium (K(eq) = 1.6) with IrH(5)(P(i)Pr(3))(2) and [WH(5)(PMe(2)Ph)(3)](-) while the same reaction of WH(6)(PMe(2)Ph)(3) with the [K(18-crown-6)](+) salt of [cis-IrH(4)(P(i)Pr(3))(2)](-) has a much larger equilibrium constant (K(eq) = 150) to give IrH(5)(P(i)Pr(3))(2) and [WH(5)(PMe(2)Ph)(3)](-); therefore, the tetrahydride anion displays an unprecedented increase (about 100-fold) in basicity with a change from [K(crypt)](+) to [K(crown)](+) countercation and a change from trans to cis stereochemistry. The acidity of the pentahydrides decrease in THF as IrH(5)(P(i)Pr(3))(2)/[K(crypt)][trans-IrH(4)(P(i)Pr(3))(2)] (pK(alpha)(THF) = 42) > IrH(5)(PCy(3))(2)/[K(crypt)][trans-IrH(4)(PCy(3))(2)] (pK(alpha)(THF) = 43) > IrH(5)(P(i)Pr(3))(2)/[K(crown)][cis-IrH(4)(P(i)Pr(3))(2)] (pK(alpha)(THF) = 44) > IrH(5)(PCy(3))(2)/[K(crown)][cis-IrH(4)(PCy(3))(2)]. The loss of PCy(3) from IrH(5)(PCy(3))(2) can result in mixed ligand complexes and H/D exchange with deuterated solvents. Reductive cleavage of P-Ph bonds is observed in some preparations of the PPh(3) complexes.     

Syntheses, structures and properties of a series of non-heme alkoxide-Fe(III) complexes of a benzimidazolyl-rich ligand as models for lipoxygenase

The treatment of Fe(ClO(4))(2)·6H(2)O or Fe(ClO(4))(3)·9H(2)O with a benzimidazolyl-rich ligand, N,N,N',N'-tetrakis[(1-methyl-2-benzimidazolyl)methyl]-1,2-ethanediamine (medtb) in alcohol/MeCN gives a mononuclear ferrous complex, [Fe(II)(medtb)](ClO(4))(2)·?CH(3)CN·?CH(3)OH (1), and four non-heme alkoxide-iron(III) complexes, [Fe(III)(OMe)(medtb)](ClO(4))(2)·H(2)O (2, alcohol = MeOH), [Fe(III)(OEt)(Hmedtb)](ClO(4))(3)·CH(3)CN (3, alcohol = EtOH), [Fe(III)(O(n)Pr)(Hmedtb)](ClO(4))(3)·(n)PrOH·2CH(3)CN (4, alcohol = n-PrOH), and [Fe(III)(O(n)Bu)(Hmedtb)](ClO(4))(3)·3CH(3)CN·H(2)O (5, alcohol = n-BuOH), respectively. The alkoxide-iron(III) complexes all show 1) a Fe(III)-OR center (R = Me, 2; Et, 3; (n)Pr, 4; (n)Bu, 5) with the Fe-O bond distances in the range of 1.781-1.816 ?, and 2) a yellow color and an intense electronic transition around 370 nm. The alkoxide-iron(III) complexes can be reduced by organic compounds with a cis,cis-1,4-diene moiety via the hydrogen atom abstraction reaction.     

Tert-butylamidinate tin(ii) complexes: high activity, single-site initiators for the controlled production of polylactide

The tin(ii) coordination chemistry of two monoanionic N,N'-bis(2,6-diisopropylphenyl)alkylamidinate ligands is described. Complexation studies with the acetamidinate, [MeC(NAr)(2)](-), (Ar = 2,6-(i)Pr(2)C(6)H(3)) are complicated by the side formation of the bis(amidinate) tin(ii) compound, [MeC(NAr)(2)](2)Sn. By contrast, the bulkier tert-butylamidinate, [(t)BuC(NAr)(2)](-), allows tin(ii) mono-halide, -alkoxide and -amide complexes to be isolated cleanly in high yields. Thus, the reaction of [(t)BuC(NAr)(2)]H with (n)BuLi and subsequent treatment with SnCl(2) generates [(t)BuC(NAr)(2)]SnCl, in ca. 70% yield. Reactions of with LiO(i)Pr, LiNMe(2) and LiNTMS(2) afford [(t)BuC(NAr)(2)]Sn(O(i)Pr), [(t)BuC(NAr)(2)]Sn(NMe(2)), and [(t)BuC(NAr)(2)]Sn(NTMS(2)), respectively. The molecular structures of complexes are reported. Complexes, and have been investigated as initiators for the ring-opening polymerisation of rac-lactide: and display characteristics of well-controlled polymerisation initiators, but high molecular weight polymer is observed with due to inefficient initiation, a consequence of the steric bulk of the NTMS(2) unit. Polymerisations with and are faster than for the corresponding beta-diketiminate tin(ii) complexes, consistent with the more open nature of the tin(ii) coordination sphere.     

New titanium complexes with symmetric or asymmetric cis-9,10-dihydrophenanthrenediamide ligands formed through sequential intramolecular C-C bond-forming reactions

A series of new titanium(IV) complexes with symmetric or asymmetric cis-9,10-dihydrophenanthrenediamide ligands, cis-9,10-PhenH(2)(NR)(2)Ti(O(i)Pr)(2) [PhenH(2) = 9,10-dihydrophenanthrene, R = 2,6-(i)Pr(2)C(6)H(3) (2a), 2,6-Et(2)C(6)H(3) (2b), 2,6-Me(2)C(6)H(3) (2c)], cis-9,10-PhenH(2)(NR(1))(NR(2))Ti(O(i)Pr)(2) [R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Et(2)C(6)H(3) (2d); R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Me(2)C(6)H(3) (2e)], and [cis-9,10-PhenH(2)(NR(1))(2)][o-C(6)H(4)(CH=NR(2))]TiO(i)Pr [R(1) = 2,6-(i)Pr(2)C(6)H(3), R(2) = 2,6-Et(2)C(6)H(3) (3a); R(1) = 2,6-(i)Pr(2)C(6)H(3), 2,6-Me(2)C(6)H(3) (3b)], have been synthesized from the reactions of TiCl(2)(O(i)Pr)(2) with o-C(6)H(4)(CH=NR)Li [R = 2,6-(i)Pr(2)C(6)H(3), 2,6-Et(2)C(6)H(3), 2,6-Me(2)C(6)H(3)]. The symmetric complexes 2a-2c were obtained from the reactions of TiCl(2)(O(i)Pr)(2) with 2 equiv of the corresponding o-C(6)H(4)(CH=NR)Li followed by intramolecular C-C bond-forming reductive elimination and oxidative coupling processes, while the asymmetric complexes 2d-2e were formed from the reaction of TiCl(2)(O(i)Pr)(2) with two different types of o-C(6)H(4)(CH=NR)Li sequentially. The complexes 3a and 3b were also isolated from the reactions for complexes 2d and 2e. All complexes were characterized by (1)H and (13)C NMR spectroscopy, and the molecular structures of 2a, 2b, 2e, and 3a were determined by X-ray crystallography.