J. Appl. Cryst.の発刊に際して

Metal-Organic Derivatives with Fluorinated Ligands as Precursors for Inorganic Nanomaterials.

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https://journals.iucr.org/e/issues/2008/06/00/ng2456/ng2456.pdf

Tetrakis(1,1,1-trifluoroacetylacetonato-κ2O,O′)zirconium(IV) toluene solvate

A series of modified, hafnium tert-butoxide ([Hf(OBut)4]) compounds (1–26) were crystallographically characterized, and representative species were then used to produce HfO2nanoparticles. This systematically varied family of [Hf(OR)4] compounds was developed from the reaction of [Hf(OBut)4] with a series of (i) Lewis basic solvents, tetrahydrofuran, pyridine, or 1-methylimidazole; (ii) simple phenols, HOC6H4(R)-2 or HOC6H3(R)2-2,6 where R = CH3, CH(CH3)2, or C(CH3)3; and (iii) complex polydentate alcohols, tetrahydrofuran methanol (H-OTHF), pyridinecarbinol (H-OPy), and tris(hydroxymethylethane) (THME-H3). The solvent-modified products were crystallographically characterized as [Hf(OBut)4(solv)n] (1–3). The phenoxide (OAr)-exchanged [Hf(OBut)4] products isolated from toluene were characterized as dimeric [Hf(OAr)n(OBut)4–n]2 (4 and 5) or [Hf(μ-OH)(OAr)3(HOBut)]2 (6 and 7) for the less sterically demanding OAr ligands and [Hf(OAr)n(OBut)4–n(HOBut)] (8 and 9) monomers for the larger OAr ligands. When Lewis ...

Synthesis and structural characterization of a family of modified hafnium tert-butoxide for use as precursors to hafnia nanoparticles.

Poly(ester-alt-ethers) can combine beneficial ether linkage flexibility and polarity with ester linkage hydrolysability, furnishing fully degradable polymers. Despite their promising properties, this class of polymers remains underexplored, in part due to difficulties in polymer synthesis. Here, a catalyzed copolymerization using commercially available monomers, butylene oxide (BO)/oxetane (OX), tetrahydrofuran (THF), and phthalic anhydride (PA), accesses a series of well-defined poly(ester-alt-ethers). A Zr(IV) catalyst is reported that yields polymer repeat units comprising a ring-opened PA (A), followed by two ring-opened cyclic ethers (B/C) (−ABB– or −ABC−). It operates with high polymerization control, good rate, and successfully enchains epoxides, oxetane, and/or tetrahydrofurans, providing a straightforward means to moderate the distance between ester linkages. Kinetic analysis of PA/BO copolymerization, with/without THF, reveals an overall second-order rate law: first order in both catalyst and butylene oxide concentrations but zero order in phthalic anhydride and, where it is present, zero order in THF. Poly(ester-alt-ethers) have lower glass-transition temperatures (−16 °C < Tg < 12 °C) than the analogous alternating polyesters, consistent with the greater backbone flexibility. They also show faster ester hydrolysis rates compared with the analogous AB polymers. The Zr(IV) catalyst furnishes poly(ester-alt-ethers) from a range of commercially available epoxides and anhydride; it presents a straightforward method to moderate degradable polymers’ properties.

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Zr(IV) Catalyst for the Ring-Opening Copolymerization of Anhydrides (A) with Epoxides (B), Oxetane (B), and Tetrahydrofurans (C) to Make ABB- and/or ABC-Poly(ester-alt-ethers)

The binuclear title compound, [Hf2(C5HF6O2)6(OH)2]·C3H6O, contains an HfIV atom which is eight coordinated and surrounded by three chelating β-diketonato 1,1,1,5,5,5-hexa­fluoro­acetyl­acetonate (hfaa) ligands and two bridging OH groups situated on a twofold rotation axis. The HfO8 coordination polyhedron shows a slightly distorted Archimedean square anti-prismatic coordination with average Hf—O, C—O, C—CMe distances of 2.19 (2), 1.26 (2) and 1.49 (2) A, respectively, and an O—Hf—O bite angle of 75.3 (5)°. Weak O—H⋯O hydrogen bonding inter­actions are observed between one of the bridging hydr­oxy groups and the disordered solvent mol­ecule.

Di-μ-hydroxido-bis[tris(1,1,1,5,5,5-hexa­fluoro­acetyl­acetonato-κ2O,O′)hafnium(IV)] acetone solvate

In the title compound, [Hf(C9H6NO)4]·2C7H8, the hafnium metal centre is coordinated by four N,O-donating bidentate quinolin-8-olate ligands arranged to give a square-anti­prismatic coordination polyhedron with a slightly distorted dodeca­hedral geometry. The average Hf—O and Hf—N distances are 2.096 (3) and 2.398 (3) A, respectively, and the average O—Hf—N bite angle is 70.99 (11)°. The crystal packing is controlled by π–π inter­actions between quinoline ligands of neighbouring mol­ecules and hydrogen-bonding inter­actions. The inter­planar distances vary between 3.138 (1) and 3.208 (2) A, while the centroid–centroid distances range from 3.576 (1) to 4.074 (1) A.

https://journals.iucr.org/e/issues/2009/12/00/bg2301/bg2301.pdf

Tetra­kis(quinolin-8-olato-κ2N,O)hafnium(IV) toluene disolvate

In the title compound, [Zr(C5H4F3O2)4]·C7H8, the Zr atom is in a square-anti­prismatic coordination geometry that comprises four O,O′-bidentate trifluoro­acetyl­acetonate ligands The O—Zr—O bite angles of the acetonate ligands range from 7527 (5) to 7541 (5)° The Zr atom is located on a twofold rotation axis

https://journals.iucr.org/e/issues/2008/06/00/hy2134/hy2134.pdf

Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')hafnium(IV) toluene disolvate.

In the title compound, [Zr(C6H4NO2)4]·2H2O, the ZrIV atom is located on a crystallographic fourfold rotoinversion axis (\overline{4}) and is coordinated by four picolinate anions with Zr—O and Zr—N distances of 2.120 (2) and 2.393 (2) A, respectively. An approximate square-anti­prismatic coordination polyhedron of the N,O-coordination ligand atoms is formed, with a distortion towards dodeca­hedral geometry. The crystal packing is stabilized by inter­molecular π–π inter­actions between adjacent picolinate rings [centroid–centroid distances = 3.271 (1) and 3.640 (2) A], as well as O—H⋯O hydrogen bonds between the solvent mol­ecules and the coordinated ligands, thereby linking the mol­ecules into a supra­molecular three-dimensional network.

https://journals.iucr.org/e/issues/2011/09/00/zq2119/zq2119.pdf

Maryke Steyn

Papers

Tetrakis(1,1,1-trifluoroacetylacetonato-κ2O,O′)zirconium(IV) toluene solvate

Di-μ-hydroxido-bis[tris(1,1,1,5,5,5-hexafluoroacetylacetonato-κ2O,O′)hafnium(IV)] acetone solvate

Tetrakis(quinolin-8-olato-κ2N,O)hafnium(IV) toluene disolvate

Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')hafnium(IV) toluene disolvate.

Tetra-kis(picolinato-κN,O)zirconium(IV) dihydrate.

Maryke Steyn

Papers

Tetrakis(1,1,1-trifluoroacetylacetonato-κ2O,O′)zirconium(IV) toluene solvate

Di-μ-hydroxido-bis[tris(1,1,1,5,5,5-hexa­fluoro­acetyl­acetonato-κ2O,O′)hafnium(IV)] acetone solvate

Tetra­kis(quinolin-8-olato-κ2N,O)hafnium(IV) toluene disolvate

Tetra-kis(1,1,1-trifluoro-acetyl-acetonato-κO,O')hafnium(IV) toluene disolvate.

Tetra-kis(picolinato-κN,O)zirconium(IV) dihydrate.

Di-μ-hydroxido-bis[tris(1,1,1,5,5,5-hexafluoroacetylacetonato-κ2O,O′)hafnium(IV)] acetone solvate

Tetrakis(quinolin-8-olato-κ2N,O)hafnium(IV) toluene disolvate