Titanium(III) Compounds with η2-Pyrazolato Ligands

Mösch‐Zanetti, Nadia C.; Krätzner, Ralph; Lehmann, Christopher; Schneider, Thomas; Usón, Isabel

doi:10.1002/(sici)1099-0682(200001)2000:1<13::aid-ejic13>3.0.co;2-n

Cited by 39 publications

(22 citation statements)

References 27 publications

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“…Three symmetrically chelating h 2 -pyrazolate (Table 1) are coordinated to scandium, with the six coordinate ScN 6 geometry closely trigonal prismatic and the pyrazolate planes parallel to the putative C 3 axis, which in turn is closely aligned to the crystallographic c axis. Although 1 has a similar molecular array to those of the recently determined [M(h 2 -tBu 2 pz) 3 ] complexes (M Al [15] or Ti [13] ), it is not isomorphous with them. In the latter pair, the three ligands are related by a three-fold axis in space group P3 Å (cf.…”

Section: Resultsmentioning

confidence: 73%

Simple Syntheses, Structural Diversity, and Tishchenko Reaction Catalysis of Neutral Homoleptic Rare Earth(II orIII) 3,5-Di-tert-butylpyrazolates—The Structures of [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln=La, Nd, Yb, Lu), and [Eu4(tBu2pz)8]

Deacon

Gitlits

Roesky³

et al. 2001

Chem. Eur. J.

124

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The homoleptic rare-earth pyrazolate complexes [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln = La, Nd, Sm, Lu), [Eu4(tBu2pz)8] and the mixed oxidation state species [Yb2(tBu2pz)5] (tBu2pz = 3,5-di-tert-butylpyrazolate) have been prepared by a simple reaction between the corresponding rare-earth metal and 3,5-di-tert-butylpyrazole, in the presence of mercury, at elevated temperatures. In addition, [Yb2(tBu2pz)6] was prepared by redox transmetallation/ligand exchange between ytterbium, diphenylmercury(II) and tBu2pzH in toluene, whilst the same reactants in toluene under different conditions or in diethyl ether gave [Yb2(tBu2pz)5]. The complexes of the trivalent lanthanoids display dimeric structures [Ln2(tBu2pz)6] (Ln = La, Nd, Yb, Lu) with chelating eta2-terminal and eta2:eta2-bridging pyrazolate coordination. The considerably smaller Sc3+ ion forms monomeric [Sc(tBu2pz)3] of putative D3h molecular symmetry, with pyrazolate ligands solely eta2-bonded. [Eu4(tBu2pz)8] is a structurally remarkable tetranuclear EuII complex with two types of europium centres in a linear array. The outer two are bonded to one terminal and two bridging pyrazolates, and the inner two are coordinated by four bridging ligands. Unprecedented mu-eta5:eta2 pyrazolate ligation is observed, with each outer Eu2+ sandwiched between two eta5-bonded pyrazolate groups, which are also eta2-linked to an inner Eu2+. The two inner Eu2+ ions are linked together by two equally occupied components of each of two symmetry related, disordered pyrazolate groups with one component eta4:eta2 bridging and one eta3:eta2 bridging. [La2(tBu2pz)6] has also been shown to be a Tishchenko reaction catalyst with several organic substrates.

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Section: Resultsmentioning

confidence: 73%

Simple Syntheses, Structural Diversity, and Tishchenko Reaction Catalysis of Neutral Homoleptic Rare Earth(II orIII) 3,5-Di-tert-butylpyrazolates—The Structures of [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln=La, Nd, Yb, Lu), and [Eu4(tBu2pz)8]

Deacon

Gitlits

Roesky³

et al. 2001

Chem. Eur. J.

124

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“…In addition, 1Ϫ3 constitute rare examples of η 2 -pyrazolato ligand coordination to d-block metal centers with partially filled d shells. [8,9] There has been one previous report of a (pyrazolato)vanadium complex, [(TpiPr 2 V(O)(µ-OH)(µ-PziPr 2 )V(O)(µ-OH)(µ-PziPr 2 )V(O)TpiPr 2 )], which was obtained by partial hydrolysis of a vanadium(IV) hydrotris(3,5-diisopropyl-1-pyrazolyl)borate complex. [16] The 3,5-diisopropylpyrazolato ligands in this complex bridge between two vanadium(IV) ions with the well-documented µ-η 1 :η 1 -coordination mode.…”

Section: Discussionmentioning

confidence: 99%

“…In this vein, Mösch-Zanetti has reported the synthesis and structure of tris(3,5-di-tert-butylpyrazolato)titanium(III) and several other (pyrazolato)titanium(III) complexes, and found η 2 -coordination of the pyrazolato ligands in these d 1 systems. [8] In addition, we have recently described the synthesis, structure, and bonding of tris(3,5-di-tert-butylpyrazolato)chromium(III) and -iron-(III). [9] These d 3 and d 5 complexes contain η 2 -pyrazolato ligands, and suggest that many transition metal complexes with partially filled d shells may be able to support η 2 -pyrazolato ligands.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Molecular Orbital Calculations of (Pyrazolato)vanadium(III) Complexes − Understanding η2-Pyrazolato Ligand Coordination on d2 Metal Centers

Gust¹,

Knox²,

Heeg³

et al. 2002

Eur. J. Inorg. Chem.

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Treatment of trichlorotris(tetrahydrofuran)vanadium(III) with (3,5-di-tert-butylpyrazolato)potassium (1, 2, or 3 equiv.) in tetrahydrofuran afforded V(tBu 2 Pz)Cl 2 (THF) 2 (48%), V(tBu 2 Pz) 2 Cl(THF) 2 (67%), and V(tBu 2 Pz) 3 (THF) (77%), respectively, as purple crystalline solids. The X-ray crystal structures of V(tBu 2 Pz)Cl 2 (THF) 2 , V(tBu 2 Pz) 2 Cl(THF) 2 , and V(tBu 2 Pz) 3 (THF) reveal six-and seven-coordinate vanadium centers with η 2 -pyrazolato ligands. Molecular orbital calculations were carried out to understand the electronic nature of

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“…105,117,118 More recently both Etter and Bernstein have studied this compound. 105,119,120 Bernstein in particularly showed that there are three polymorphs, designated as α, β and δ, and a hydrate which is more than likely the form designated as γ in the 1899 and Groth papers ( Table 2.4).…”

Section: Npumentioning

confidence: 99%

Anion-tuning of supramolecular gel properties

2009

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Titanium(III) Compounds with η2-Pyrazolato Ligands

Cited by 39 publications

References 27 publications

Simple Syntheses, Structural Diversity, and Tishchenko Reaction Catalysis of Neutral Homoleptic Rare Earth(II orIII) 3,5-Di-tert-butylpyrazolates—The Structures of [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln=La, Nd, Yb, Lu), and [Eu4(tBu2pz)8]

Simple Syntheses, Structural Diversity, and Tishchenko Reaction Catalysis of Neutral Homoleptic Rare Earth(II orIII) 3,5-Di-tert-butylpyrazolates—The Structures of [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln=La, Nd, Yb, Lu), and [Eu4(tBu2pz)8]

Synthesis, Structure, and Molecular Orbital Calculations of (Pyrazolato)vanadium(III) Complexes − Understanding η2-Pyrazolato Ligand Coordination on d2 Metal Centers

Anion-tuning of supramolecular gel properties

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