Alkoxy Oxygen Atom Research Articles

Tungsten minerals flotation with 4-alkoxy benzohydroxamic acid: The structure-performance relationship of its C3 derivatives

To improve the flotation recovery of tungsten minerals, 4-alkoxy benzohydroxamic acids containing C3 alkyl (C3OBs), namely 4-propoxy benzohydroxamic acid (POB), 4-iso-propoxy benzohydroxamic acid (IPOB) and 4-allyloxy hydroxamic acid (AOB), were designed as scheelite and wolframite collectors. The micro-flotation results uncovered that C3OBs exhibited stronger collecting ability towards Pb(Ⅱ)-activated scheelite and wolframite than benzohydroxamic acid (BHA) and the collecting ability of C3OBs was in sequence of POB > IPOB > AOB. The density functional theory (DFT) calculation indicated that the alkoxy oxygen atom of C3OBs contributed to their highest occupied molecular orbital (HOMO), and the HOMO energy followed the order as IPOB > POB > AOB > BHA. The higher HOMO energy, the stronger electron-donating activity. Nevertheless, IPOB didn’t return the highest flotation recovery of tungsten minerals. On the other hand, the hydrophobicity of these four hydroxamate collectors was in sequence of POB > IPOB > AOB > BHA, corresponding to the results of contact angle, micro-flotation and adsorption capacity. Therefore, the hydrophobization of the four hydroxamate collectors played a key role in their flotation performance to the Pb(II)-activated scheelite and wolframite. Moreover, this work offered a new approach for developing superior collectors.

Novel Heteroleptic Tin(II) Complexes Capable of Forming SnO and SnO2 Thin Films Depending on Conditions Using Chemical Solution Deposition.

A new heteroleptic complex series of tin was synthesized by the salt metathesis reaction of SnX2 (X = Cl, Br, and I) with aminoalkoxide and various N-alkoxy-functionalized carboxamide ligands. The complexes, [ClSn(dmamp)]2 (1), [BrSn(dmamp)]2 (2), and [ISn(dmamp)]2 (3), were prepared from the salt metathesis reaction of SnX2 with one equivalent of dmamp; [Sn(dmamp)(empa)]2 (4), [Sn(dmamp)(mdpa)]2 (5), and [Sn(dmamp)(edpa)]2 (6) were prepared via the salt metathesis reaction using complex 2 with one equivalent of N-alkoxy-functionalized carboxamide ligand. Complexes 1–5 displayed dimeric molecular structures with tin metal centers interconnected by μ2–O bonding via the alkoxy oxygen atom. The molecular structures of complexes 1–5 showed distorted trigonal bipyramidal geometries with lone pair electrons in the equatorial position. Using complex 6 as a tin precursor, SnOx films were deposited by chemical solution deposition (CSD) and subsequent post-deposition annealing (PDA) at high temperatures. SnO and SnO2 films were selectively obtained under controlled PDA atmospheres of argon and oxygen, respectively. The SnO films featured a tetragonal romarchite structure with high crystallinity and a preferred growth orientation along the (101) plane. They also exhibited a lower transmittance of >52% at 400 nm due to an optical band gap of 2.9 eV. In contrast, the SnO2 films exhibited a tetragonal cassiterite crystal structure and an extremely high transmittance of >97% at 400 nm was observed with an optical band gap of 3.6 eV.

Synthesis of Heteroleptic Zinc Complexes Containing Aminoalkoxide and β‐Diketonate Ligands

AbstractNew heteroleptic complexes of zinc were designed and synthesized using aminoalkoxide and β‐diketonate ligands. The complexes, [Zn(dmamp)(tmhd)]2 (1), [Zn(dmamp)(acac)]2 (2), [Zn(dmamp)(hfac)]2 (3), [Zn(dmamb)(tmhd)]2 (4), [Zn(dmamb)(acac)]2 (5), and [Zn(dmamb)(hfac)]2 (6), were synthesized by controlled acid‐base reactions between [EtZn(aminoalkoxide)]2 and β‐diketonate ligands. Single crystal x‐ray diffraction showed that complexes 1−4 and 6 exist as dimeric molecular structures with the zinc metal centers interconnected by the alkoxy oxygen atom via μ2‐O bonding and their gemetries exhibit distorted trigonal bipyrimidal. TGA curves of complexes 3 and 6 showed sharp weight losses in a single step with very low residues, which confirmed the excellent vaporization and thermal stability.

N–H⋯O hydrogen bonding to the alkoxy oxygen of a carboxylic ester group: crystal structures of methyl 2,6-diaminobenzoate and its derivatives

Molecules with hydrogen bonds from amino groups to both oxygens of a carboxylic ester are described, and other examples of hydrogen bonding to an ester's alkoxy oxygen atom are highlighted.

Synthesis, Crystal Structure, Mesophase Behaviour and Optical Property of Azo-ester Bridged Compounds

Azo-ester mesogen containing two liquid crystalline compounds C1-C2 having polymerizable acrylate functional group as the terminal were designed and synthesized. The chemical structures and purity of the synthesized compounds were confirmed by different spectroscopic techniques such as FT-IR, 1H NMR and 13C NMR. X-ray crystal structure showed that compound C1 exhibited more stable E configuration with two bulky groups in the opposite sides of the N=N double bond motifs. The 1, 2-diphenyldiazene fragment in the structure of C1 is essentially planar with RMS deviation from planarity of 0.0555 Å. Analysis of the crystal packing of compound C1 revealed its intriguing supramolecular sheet-like multilayer molecular packing stabilized by C-H…O interaction involving the phenyl and acryloyl hydrogen with the carbonyl oxygen and alkoxy oxygen atoms. Thermogravimetric investigation demonstrated that both of the compounds exhibited excellent thermal stability and their thermal degradation was influenced by the terminal substituent. The DSC and POM studies confirmed that compounds C1-C2 exhibited enantiotropic liquid crystalline mesophase behaviour. Optical investigations demonstrated that both of the compounds showed strong absorption band around 300-420 nm and exhibited blue fluorescence emission.

New Heteroleptic Cobalt Precursors for Deposition of Cobalt-Based Thin Films.

A new series of heteroleptic complexes of cobalt were synthesized using aminoalkoxide and β-diketonate ligands. The complexes, [Co(dmamp)(acac)]2 (3), [Co(dmamp)(tfac)]2 (4), [Co(dmamp)(hfac)]2 (5), [Co(dmamp)(tmhd)]2 (6), and [Co(dmamb)(tmhd)]2 (7), were prepared by two-step substitution reactions and studied using Fourier transform infrared spectroscopy, mass spectrometry, elemental analysis, and thermogravimetric analysis (TGA). Complexes 3–7 displayed dimeric molecular structures for all of the complexes with cobalt metal centers interconnected by μ2-O bonding by the alkoxy oxygen atom. TGA and a thermal study of the complexes displayed high volatilities and stabilities for complexes 6 and 7, with sublimation temperatures of 120 °C/0.5 Torr and 130 °C/0.5 Torr, respectively.

Self-Assembly of Cations in Aqueous Solutions of Hydroxyl-Functionalized Ionic Liquids: Molecular Dynamics Studies.

The effect of presence of a hydroxyl-functionalized alkyl chain of varying carbon number on the self-assembly of cations in aqueous solutions of 1-(n-hydroxyalkyl)-3-decylimidazolium bromide (where the alkyl groups are ethyl, butyl, heptyl, and decyl) has been studied using atomistic molecular dynamics simulations. Spontaneous self-assembly of cations to form aggregates with hydrophobic core and hydrophilic surface is observed. The shape of the aggregates changes from quasispherical in the case of cations with hydroxyheptyl or smaller substituent chain, to a thin film like intercalated aggregate in the case of cations with hydroxydecyl chain. Cations with hydroxydecyl substituent chain exhibit long-range spatial correlations, and the anions are associated with cations to a greater extent due to the higher surface charge density of the aggregate. The ordered film like aggregate is stabilized by the dispersion interactions between the intercalated substituent chains and the intermolecular hydrogen bonds formed between the alkoxy oxygen atoms and the hydrogen atoms of the imidazolium ring. The cations form less compact aggregates with lower aggregation number than their nonhydroxyl analogues in the corresponding aqueous solutions. The intracationic and aggregate structures are governed by the length of the hydroxyalkyl chain.

Heterometallic Pentanuclear [Ni4Ln] (LnIII = Gd, Tb, Dy, Ho) Complexes: Accidental Orthogonality Leading to Ferromagnetic Interactions

AbstractThe reaction of 6‐formyl‐2‐(hydroxymethyl)‐4‐methylphenol (LH2) with NiII and LnIII salts afforded a series of heterometallic pentanuclear compounds [Ni4Ln(L)4(OAc)2(MeOH)4](NO3)(MeOH) [LnIII = Gd (1), Dy (2), Tb (3), Ho (4)]. Four dianionic L2– ligands and two acetate anions hold together four NiII and one LnIII ion to form a Ni4Ln core possessing a distorted tetrahedral geometry. All the NiII ions are hexacoordinate (6 O) with a distorted octahedral geometry whereas the LnIII ion is octacoordinate (8 O) with a distorted square‐antiprism geometry. All the NiII ions are connected to the central LnIII ion through μ2 bridging of one deprotonated phenolic oxygen and two deprotonated alkoxy oxygen atoms. The magnetic properties of 1–4 were investigated in the temperature range 2–300 K. The magnetic properties of 1 were fitted by using a Hamiltonian containing isotropic exchange, NiII local zero‐field‐splitting, and Zeeman effects (Ĥ = Ĥexchange + Ĥzfs + Ĥzeeman). The molecular structures of 1–4 reveal that the Ni–O–Ln angle is around 89° whereas the Ni–O–Ni angle is about 96°. Because of this accidental orthogonality, ferromagnetic interactions between the nearest‐neighbor NiII ions and between NiII and LnIII ions have been observed. The observed J values are 0.34 and 1.88 cm–1 between GdIII–NiII and NiII–NiII, respectively.

A density functional theory model of mechanically activated silyl ester hydrolysis.

To elucidate the mechanism of the mechanically activated dissociation of chemical bonds between carboxymethylated amylose (CMA) and silane functionalized silicon dioxide, we have investigated the dissociation kinetics of the bonds connecting CMA to silicon oxide surfaces with density functional calculations including the effects of force, solvent polarizability, and pH. We have determined the activation energies, the pre-exponential factors, and the reaction rate constants of candidate reactions. The weakest bond was found to be the silyl ester bond between the silicon and the alkoxy oxygen atom. Under acidic conditions, spontaneous proton addition occurs close to the silyl ester such that neutral reactions become insignificant. Upon proton addition at the most favored position, the activation energy for bond hydrolysis becomes 31 kJ mol(-1), which agrees very well with experimental observation. Heterolytic bond scission in the protonated molecule has a much higher activation energy. The experimentally observed bi-exponential rupture kinetics can be explained by different side groups attached to the silicon atom of the silyl ester. The fact that different side groups lead to different dissociation kinetics provides an opportunity to deliberately modify and tune the kinetic parameters of mechanically activated bond dissociation of silyl esters.

Layered transition metal carboxylates: synthesis, structural aspects and observation of multi-step magnetic transition through phase diagram

Two new layered transition metal carboxylate frameworks, [Co3(L)2(H2O)6]·2H2O () and [Ni3(L)2(H2O)6]·2H2O () (L = tartronate anion or hydroxymalonic acid), have been synthesized and characterized by X-ray single crystal analysis. Both compounds have similar 2D structures. In both compounds there are two types of metal centers where one center is doubly bridged by the alkoxy oxygen atoms through μ2-O bridging to form a 1D infinite chain parallel to the crystallographic b-axis with the corners shared between the metal polyhedra. Magnetic susceptibility measurements revealed the existence of antiferromagnetic short range correlations between Co(Ni) intra-chain metal centers (with exchange constants JCo = -22.6 and JNi = -35.4 K). At low temperatures, long range order is observed in both compounds at Néel temperatures of 11 (for ) and 16 (for ) K, revealing that other exchange interactions, rather than the intra-chain ones, play a role in these systems. Whereas compound has an antiferromagnetic ground state, compound exhibits a ferromagnetic component, probably due to spin canting. Isothermal magnetization data unveiled a rich phase diagram with three metamagnetic phase transitions below 8 K in compound .

A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt) 3, Ge(OEt) 4 and Ti(OEt) 4 are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu) 4. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.

Transformations of N-Confused Porphyrin Triggered by Insertion of Silicon(IV)

N-confused porphyrin, 5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin, dissolved in triethylamine reacts with dichloromethylsilane yielding the methylsilicon(IV) complex of 5,10,15,20-tetraaryl-2-aza-21-hydroxy-21-carbaporphyrin. Addition of aldehydes or ketones (acetone, acetaldehyde acetophenone, butanone, propanal, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, terephthaldehyde) into the insertion mixture triggered the profound transformation of N-confused porphyrin to form the methylsilicon(IV) complex of N-fused porphyrin derivative substituted at the inner C(9) position by a hydroxyalkyl moiety derived from aldehyde or ketone. The macrocyle is structurally related to an aromatic N-fused inner phlorin while the coordination polyhedron of bound silicon resembles the trigonal bipyramid. The macrocyclic ligand coordinates in the facial mode as the three pyrrolic nitrogen donors lie at the vertices of the single trigonal face. The meridional positions of the trigonal bipyramid are occupied by two pyrrolic nitrogen donors and a sigma-methyl ligand. The coordination sphere is completed by apical coordination of the alkoxy oxygen atom derived from alkanal or alkonone. The incorporation of aldehydes and ketones is stereoselective. Acidic desililation of alkanal compounds yields two aromatic N-confused porphyrin derivatives, that is, 3-(1-hydroxyalkyl)-5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin and its oxidation product 3-alkanoyl-5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin. The acid triggered desililation of ketone derivatives produces the equimolar amounts of N-confused porphyrin and ketone. The first spectroscopically identified step involves the protonation of the C(7) position affording the non-aromatic silicon(IV) complex. The density functional theory (DFT) has been applied to model the molecular and electronic structure of all species identified in the course of silicon insertion into the N-confused and N-fused porphyrin.

Ferromagnetic exchange coupling in a new bis(μ-chloro)-bridged copper(II) Schiff base complex: Synthesis, structure, magnetic properties and catalytic oxidation of cycloalkanes

Abstract A new (μ-chloro)-bridged complex [Cu(HL)Cl]2 · H2O (1) with the Schiff base ligand H2L, [2-((E)-(2-hydroxyethylimino)methyl)-4-bromophenol], has been synthesized and characterized by elemental analysis, IR, UV–Vis and EPR spectroscopic studies. X-ray diffraction studies show that 1 is a binuclear CuII complex with a pair of chlorine atoms bridging the copper atoms in a central Cu2Cl2 core. Each copper atom in 1 adopts a distorted square-pyramidal geometry with the imine nitrogen atom, alkoxy and phenoxy oxygen atoms from the Schiff base ligand and a bridging chlorine atom constructing the basal plane, while the apical position of the pyramid is occupied by the other bridging chlorine atom. Variable temperature susceptibility measurements show that complex 1 presents the highest ferromagnetic coupling [J = +43.2(5) cm−1] reported till date in any doubly chloro-bridged CuII dimer, and a weak interdimer antiferromagnetic coupling [J′ = -0.276(8) cm−1]. The complex also exhibits high catalytic activity towards the oxidation of hydrocarbons using H2O2 as terminal oxidant.

Factors determining the pattern of a hydrogen‐bonding network in the diastereomeric salts of 1‐arylethylamines with enantiopure P‐chiral acids

In order to clarify factor(s) determining the pattern of a hydrogen-bonding network in the diastereomeric salts of 1-arylethylamines (1) with enantiopure P-chiral acids, three kinds of enantiopure P-chiral alkylphenylphosphinothioic acids (3) were synthesized, and their chiral recognition abilities for racemic 1 were examined. The characteristics of the diastereomeric salt crystals of 1 with 3 were then studied on the basis of their X-ray crystallographic analyses. Statistical analysis on the molecular conformations observed in the diastereomeric salts with 3 as well as those with P-chiral O-alkyl arylphosphonothioic acids (2), which have a chemical structure similar to that of 3, and molecular orbital calculations for 2 and 3 in a gas phase revealed that the torsion angle between the aromatic plane and the P--O(alkoxy in 2) or P--C(alkyl in 3) plays an important role in determining the pattern of a hydrogen-bonding network in the diastereomeric salts, either a closed globular cluster or an infinite 2(1) column type. The calculations also indicated that there is a hydrogen-bonding-like interaction between the ammonium hydrogen atom of 1-arylethylammonium cations and the P--O(alkoxy) oxygen atom of phosphonothioate anions in the clusters.

Design principles to tune the optical properties of 1,3,4-oxadiazole-containing molecules

We have synthesized a series of oxadiazole compounds and ethynylene analogs. Our data reveal that the ring is both optically transparent in the visible range and fully conjugating while we have also discovered the presence of a non-radiative mechanism active in molecules containing common para-dialkoxy substituents adjacent to the oxadiazole ring(s). This structure leads to a greatly reduced quantum yield, in our example dropping from 95.0% to 48.0%. Through our thorough study we have revealed evidence that this is the result of a repulsive interaction between the oxadiazole and the adjacent alkoxy oxygen atom, which we believe prevents excited-state planarity. This quantum yield reduction is preventable through the design principles presented here.

Synthesis and structural studies of heteroleptic complexes of ytterbium(III) involving aryloxy- or alkoxy- and cyclopentadienyl ligands

Treatment of tris-cyclopentadienyl-ytterbium in thf with one equivalent of 2,6-di( tert-butyl)phenol, N, N-dimethyl-2-aminoethanol or N, N-diethyl-2-aminoethanol resulted in substitution of one cyclopentadienyl ligand and formation of [YbCp 2(O-C 6H 3 t Bu-2,6)(thf)] ( 1), [{YbCp 2(μ-OCH 2CH 2NMe 2)} 2] ( 2) or [{YbCp 2(μ-OCH 2CH 2NEt 2)} 2] · (thf) 2 ( 3), respectively. All compounds were characterised by spectroscopic and X-ray crystallographic techniques, the latter two also being studied by variable temperature 1H NMR spectroscopy. Compound ( 1) is mononuclear with the Yb centre bound by two η 5-cyclopentadienyl ligands one O-bound thf and an O-bound phenoxy ligand. Compounds ( 2) and ( 3) are centrosymmetric dimers with the Yb centre bound by two η 5-cyclopentadienyl ligands, while the bidentate ligands chelate the metal centre and also bridge to the adjacent Yb through the alkoxy oxygen atom. Variable temperature 1H NMR studies on compounds ( 2) and ( 3) show a solution-state equilibrium between the dimeric solid-state structure and one with the nitrogen atoms non-bound to Yb.

Crystal and Molecular Structure of Cu(II) Bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate)

A new compound from the series of alkoxyketoiminates, Cu(II) bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate), has been synthesized and studied by X-ray crystallography. Crystal data for CuO4N2C20H36: a=10.154(1), b=9.921(1), c=11.684(2) A, β=96.17(1)°, space group P21/c, Z=2, dcalc =1.226 g/cm3, R=0.037. The structure is molecular and built from isolated trans-complexes. The copper atom has a plane square environment of two oxygen atoms (Cu–O 1.93 A) and two nitrogen atoms (Cu–N 1.90 A). The O–Cu–N chelate angle is 91.7°. The complex has an intramolecular hydrogen bond, N–H...O 2.16 A, involving the alkoxy oxygen atom. The molecular packing in the crystal is close to that of copper(II) dipivaloylmethanate. The calculated van der Waals intermolecular interaction energies and thermogravimetric characteristics of the complexes are compared.

Structural, electronic, and magnetic consequences of O-carbonyl vs O-alkoxy ester coordination in new dicopper complexes containing the Cu2(mu-Cl)2 core.

The complexes [Cu2(mu-Cl)2(Cl)2(L)2] (L = dialkylpyridine-2,6-dicarboxylate; R = Et, L = depc, 1; R = i-Pr, L = dppc, 2) have been prepared and their magnetic properties studied. The crystal structures of complexes 1 and 2 have been solved. Compound 1 belongs to the P space group with Z = 2, a = 8.3020(10) A, b = 9.2050(10) A, c = 10.065(2) A, alpha = 99.040(10), beta = 100.810(10), and gamma = 106.502(10) whereas 2 belongs to the C2/c space group with Z = 8, a = 11.6360(10) A, b = 25.906(3) A, c = 11.76579(10) A, and beta = 107.900(10). The different alkyl ester substitutes produce substantial structural and electronic differences. The Cu2Cl2 core geometry is planar for 1 whereas it adopts a butterfly shape in the case of 2. Furthermore, in 2 the dppc ligand coordinates only by the carbonyl oxygen atoms whereas in 1 the depc ligand coordinates through carbonyl and alkoxy oxygen atoms. Magnetic susceptibility data show a ferromagnetic coupling between the two Cu(II) centers in both cases (J = 39.9(6) cm(-1) for 1, and J = 51.3(5) cm(-1) for 2) with very weak antiferromagnetic interactions (J ' = -0.59 cm(-1) and -0.57 cm(-1) for 1 and 2, respectively). Theoretical calculations at the extended Hückel level have also been carried out to further understand the electronic nature of complexes 1 and 2.

Design of selective thrombin inhibitors based on the (R)-Phe-Pro-Arg sequence.

Potent and selective inhibitors of thrombin were sought based on the (R)-Phe-Pro-Arg sequence. The objective was to generate similar binding interactions to those achieved by potent competitive inhibitors of the argatroban type, so eliminating the need for covalent interaction with the catalytic serine function, as utilized by aldehyde and boronic acid type inhibitors. Improving the S(1) subsite interaction by substitution of arginine with a 4-alkoxybenzamidine residue provided potent lead 2 (K(i) = 0.37 nM). Though an amide bond, which H-bonds to the active site, is lost, modeling indicated that a new H-bond is generated between the alkoxy oxygen atom and the catalytic Ser-195 hydroxyl group. Substitution of the benzamidine system by 1-amidinopiperidine then gave compound 4, which provided a further gain in selectivity over trypsin. However, previous work had shown that these compounds were likely to be too lipophilic (Log D +0.4 and +0.2, respectively) and to suffer rapid hepatic extraction, presumably via biliary elimination. Accordingly, both proved short-acting when administered intravenously to rats and showed poor activity when given intraduodenally. The aim was then to reduce lipophilicity below a log D of -1.2, which in a previously reported series had been effective in preventing rapid clearance. It was anticipated that compounds of this type would rely on the cation selective paracellular route of absorption from the gastrointestinal tract. Potent polar analogues with selectivity >1000 over trypsin were obtained. The best in vivo activity was shown by compound 12. However, in the final analysis, its oral bioavilability proved poor, relative to analogues with similar physicochemical properties derived from argatroban, consistent with the hypothesis that molecular shape is an additional important determinant of paracellular absorption.

Alkaline-earth metal fluoroalkoxide complexes with multi-coordinated polyether appendage: synthesis and characterization

Four alkaline-earth metal alkoxide complexes of formula [M(meak) 2] ( 1, M=Sr; 2, M=Ba) and [M(biak) 2] 2 ( 3, M=Sr; 4, M=Ba) were synthesized by the reaction of polyether substituted flouroalcohols, (meak)H=HOC(CF 3) 2CH 2(OCH 2CH 2) 2OMe and (biak)H=HOC(CF 3) 2CH 2OCH 2CH 2N(CH 2CH 2OMe) 2, with metal source reagents Sr(OPr i) 2 and BaH 2, respectively. These complexes were characterized by 1H and 19F NMR spectroscopies and single crystal X-ray diffraction studies. The coordination geometry of 1 is best described as distorted trigonal dodecahedron, while complex 2 shows a similar coordination geometry, but possesses a H 2O solvate linked to the alkoxy oxygen atom of the chelating meak ligands through H-bonding. Complexes [Sr(biak) 2] 2 ( 3) and [Ba(biak) 2] 2 ( 4) exist as dimers in the solid state in which the metal centers are linked by two bridging alkoxy oxygen atoms and encapsulated by a total of nine heteroatoms composed of a distorted tricapped trigonal prismatic geometry. Variable temperature 19F NMR studies of all complexes show simultaneous existence of two isomers in solution. Pyrolysis of these four complexes in air affords the expected SrF 2 and BaF 2 powders.