Access to the nonaqueous polar solution phase chemistry of discrete octahedral ZrF62−: Preparation and crystal structure of [P(C6H5)4]2 ZrF6, 2H2O

Larsen, Jan; Boubekeur, Kamal; Batail, Patrick; Lucas, Jacques

doi:10.1016/0025-5408(89)90047-0

Cited by 2 publications

(3 citation statements)

References 11 publications

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“…For example, because TiCl 4 reacts with many solvents that solubilize Ph 4 PCl (such as CH 3 CN), 2 was prepared in two steps from commercially available (NH 4 ) 2 TiF 6 (Scheme 2). First, compound 1 was prepared in low crystalline yield (22%) using a modification of the published procedure for (Ph 4 P) 2 ZrF 6 , 43 which involved a cation exchange reaction between (NH 4 ) 2 TiF 6 and Ph 4 PCl. The product 1 was precipitated from H 2 O, dried at elevated temperature under vacuum, and crystallized from CH 3 CN.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Compound 1 was synthesized using a modification of a previously published procedure . (NH 4 ) 2 TiF 6 (0.21 g, 1.05 mmol) and Ph 4 PCl (0.78 g, 2.09 mmol) were each dissolved in boiling water (10 mL), and the solutions were stirred together.…”

Section: Methodsmentioning

confidence: 99%

“…Compound 1 was synthesized using a modification of a previously published procedure. 43 (NH 4 ) 2 TiF 6 (0.21 g, 1.05 mmol) and Ph 4 PCl (0.78 g, 2.09 mmol) were each dissolved in boiling water (10 mL), and the solutions were stirred together. The resulting solution was allowed to cool and stored at room temperature for 24 h, which resulted in formation of white crystals.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)

Minasian

Boland²,

Feller³

et al. 2012

Inorg. Chem.

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High-purity syntheses are reported for a series of first, second, and third row transition metal and actinide hexahalide compounds with equivalent, noncoordinating countercations: (Ph(4)P)(2)TiF(6) (1) and (Ph(4)P)(2)MCl(6) (M = Ti, Zr, Hf, Th, U, Np, Pu; 2-8). While a reaction between MCl(4) (M = Zr, Hf, U) and 2 equiv of Ph(4)PCl provided 3, 4, and 6, syntheses for 1, 2, 5, 7, and 8 required multistep procedures. For example, a cation exchange reaction with Ph(4)PCl and (NH(4))(2)TiF(6) produced 1, which was used in a subsequent anion exchange reaction with Me(3)SiCl to synthesize 2. For 5, 7, and 8, synthetic routes starting with aqueous actinide precursors were developed that circumvented any need for anhydrous Th, Np, or Pu starting materials. The solid-state geometries, bond distances and angles for isolated ThCl(6)(2-), NpCl(6)(2-), and PuCl(6)(2-) anions with noncoordinating counter cations were determined for the first time in the X-ray crystal structures of 5, 7, and 8. Solution phase and solid-state diffuse reflectance spectra were also used to characterize 7 and 8. Transition metal MCl(6)(2-) anions showed the anticipated increase in M-Cl bond distances when changing from M = Ti to Zr, and then a decrease from Zr to Hf. The M-Cl bond distances also decreased from M = Th to U, Np, and Pu. Ionic radii can be used to predict average M-Cl bond distances with reasonable accuracy, which supports a principally ionic model of bonding for each of the (Ph(4)P)(2)MCl(6) complexes.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)

Minasian

Boland²,

Feller³

et al. 2012

Inorg. Chem.

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Chapter 8. Ti, Zr, Hf

Cotton¹

1990

Annu. Rep. Prog. Chem., Sect. A

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The literature for 1989-90, has been covered though much of the organometallic chemistry of these elements in particular is not reviewed here. Particular trends discernible are the intense activity in the field of alkoxides and increased success in the chemistry of the lower oxidation states of zirconium in particular. Halides and their ComplexesThe halide ZrI, has a chain structure' involving infinite chains of confacial ZrI, octahedra, distorted because of Zr-Zr pairing (Zr-Zr = 3.17,3.50 A). The reduction of TiBr, by Ti and A1 is reported' to afford respectively a-TiBr, and Ti(A1Br4)*; structures are reported for them and for HfF,., ZrC1, reacts4 with N204 to give Zr( NO3),. Structures are reported' foi a whole range of zirconium chloride cluster phases stabilized by interstitial atoms (H, B, C, Be, Fe) which can form derivatives with suitable Lewis bases. Structures like that of (Zr,Cl,,Be)( EtNH,), (Figure 1) are related to that of the well established NbgC112~+ systems.New complexes of trivalent zirconium and hafnium are M2C16 ( Pri2PCH2CH2PPri2), (M = Zr, Hf) and Hf,CI,( PMe'Ph), (Figure 2) prepared by reduction of the tetrachlorides in the presence of the ligand., They are diamagnetic, with a single metal-metal bond (around 3.09 A).ZrC1, (pinacolone) ,7 HfCl,(THF), ,8 CrCl,( MeCN), ,9 and TiC1,(Me3C.NC), l o are all cis-in the solid state. Among a range of titanium complex species character-

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Access to the nonaqueous polar solution phase chemistry of discrete octahedral ZrF62−: Preparation and crystal structure of [P(C6H5)4]2 ZrF6, 2H2O

Cited by 2 publications

References 11 publications

Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)

Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)

Chapter 8. Ti, Zr, Hf

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Access to the nonaqueous polar solution phase chemistry of discrete octahedral ZrF62−: Preparation and crystal structure of [P(C6H5)4]2 ZrF6, 2H2O

Cited by 2 publications

References 11 publications

Synthesis and Structure of (Ph4P)2MCl6(M = Ti, Zr, Hf, Th, U, Np, Pu)

Synthesis and Structure of (Ph4P)2MCl6(M = Ti, Zr, Hf, Th, U, Np, Pu)

Chapter 8. Ti, Zr, Hf

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Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)

Synthesis and Structure of (Ph₄P)₂MCl₆(M = Ti, Zr, Hf, Th, U, Np, Pu)