Phosphato, Chromato, and Perrhenato Complexes of Titanium(IV) and Zirconium(IV) Containing Kläui's Tripodal Ligand

Yi, Xiao‐Yi; Zhang, Qian‐Feng; Lam, Tony C.H.; Chan, Eddie Y. Y.; Williams, Ian D.; Leung, Wa‐Hung

doi:10.1021/ic051329u

Cited by 23 publications

(9 citation statements)

References 41 publications

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“…2 ppm), and the hydride stretching feature in the IR absorbance spectrum is significantly broadened in comparison to those observed in the spectra of 15 and 16 . While a number of hetero-multi-metallic transition metal complexes containing bridging oxo linkages to zirconium have been reported, we believe that the reaction to form 17 represents a novel means of constructing this moiety. − Additionally, previous examples of oxo-bridged Re–Zr multimetallic complexes invariably involve the binding of a perrhenate anion (ReO 4 – ) to a ligated Zr center . The derivatization of 17 to form a Zr–alkyl linkage by the displacement of the chloride ligand was attempted several times.…”

Section: Resultsmentioning

confidence: 99%

“…68−70 Additionally, previous examples of oxo-bridged Re−Zr multimetallic complexes invariably involve the binding of a perrhenate anion (ReO 4 − ) to a ligated Zr center. 71 The derivatization of 17 to form a Zr−alkyl linkage by the displacement of the chloride ligand was attempted several times. The inclusion of a strongly basic group was hypothesized to possibly lead to the deprotonation of the Re hydride, formally reducing this bimetallic system and facilitating the formation of Re−Zr bonds.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions

et al. 2020

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We present a wide range of reactivity studies focused on the rhenium(V) oxo imido complex (DippN)(O)Re(BDI) (1, Dipp = 2,6-diisopropylphenyl and BDI = N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). This complex, which was previously shown to possess a highly polarized Re oxo moiety, has proven to be a potent nucleophile and a valuable precursor to a variety of rare structural motifs in rhenium coordination complexes. For example, the Re oxo moiety of 1 undergoes [2 + 2] cycloadditions with carbodiimides, isocyanates, carbon dioxide, and isothiocyanates at room temperature. In the case of CO2, the cycloadduct with 1 (a carbonate complex) undergoes the facile ejection of CO2, demonstrating that this binding process is reversible. In the case of isothiocyanate, chalcogen metathesis with 1 takes place readily as the inclusion of a second equivalent of substrate in the reaction mixture rapidly yields a dithiocarbamate complex. This metathesis process was extended to the reactivity of 1 with phosphine chalcogenides, leading to the isolation of terminal sulfido imido and selenido imido complexes. Attempts to complete this series and generate the analogous terminal telluride led to the formation of a bidentate tritelluride (Te3 2–) complex. Triethylphosphine could only undergo oxygen atom transfer (OAT) with 1 under pressing thermal conditions that also led to C–N cleavage of the BDI ligand. In contrast, OAT between 1 and CO or 2,6-xylylisocyanide (XylNC) was found to be much more facile, proceeding within seconds at room temperature. While the addition of excess CO led to a rhenium(III) imido dicarbonyl complex, we found that the addition of 2 equiv of XylNC was necessary to promote OAT, resulting in the isolation of a rare example of a stable metal isocyanate complex. Our experimental observations of CO and XylNC and their OAT reactions with 1 inspired a mechanistic computational study to probe the intermediates and kinetic barriers along these reaction pathways. Finally, we describe 1,2-additions of both protic and hydridic substrates with the Re oxo moiety of 1, which most notably led to the syntheses of an uncommon example of a terminal rhenium hydroxide complex and an oxo-bridged Re–O–Zr hetero-bi-metallic complex that was generated using Schwartz’s reagent (Cp2ZrHCl). A brief discussion of a potential alternative route to 1 is also presented.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions

et al. 2020

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“…The structure of the trinuclear zirconium cation cluster is close to C 3V -symmetry with the diphenyl phosphate ligands orientated to one face and the l 2 -OH groups to the other. The typical Zr-(l 2 -OH) single bond lengths [19]. Taking the centroid of the C 5 H 5 rings as occupying one co-ordination site and the l 3 -O ligand trans orientated, the zirconium atoms are all in distorted octahedral environment.…”

Section: X-ray Crystallographymentioning

confidence: 99%

Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

Zhang

Wang

et al. 2010

Struct Chem

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A series of six-coordinate ''half-sandwich'' zirconocene phosphates and phosphonates have been synthesized by the reaction of Cp 2 ZrCl 2 with (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid under different conditions. All of the complexes were characterized by elemental analysis, FT-IR and NMR ( 1 H, 13 C) spectroscopy. Except for complex 3, the structures of complexes 1, 2, 4, 5, and 6 were confirmed by X-ray crystallography. The structure analyses reveal that complexes 1, 2, and 3 are trinuclear complexes with fascinating l 3 -oxygen bridging ligands, central to a Zr-O backbone (Cp 2 ZrCl 2 :ligand is 1:1) while complexes 4, 5, and 6 are centrosymmetric dinuclear complexes built up about the trapezoidal Zr 2 (l 2 -OH) 2 unit (Cp 2 ZrCl 2 :ligand is 1:2).

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“…In addition, we found that the fluoride ligands in [L OEt ZrF 3 ] (1) can be removed easily by reacting with trimethylsilyl reagents. For example, treatment of complex 1 with trimethylsilyl perrhenate and triflate led to formation of [L OEt Zr(H 2 O)(ReO 4 ) 3 ] and [L OEt Zr(OTf) 3 ], respectively [23]. This prompted us to synthesize aqua-free Zr IV sulfato complexes from complex 1 and bis(trimethylsilyl) sulfate.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structures of zirconium(IV) hydrogensulfato and carboxylato complexes with Kläui’s oxygen tripodal ligand

Zhang

Williams

et al. 2009

Journal of Organometallic Chemistry

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Phosphato, Chromato, and Perrhenato Complexes of Titanium(IV) and Zirconium(IV) Containing Kläui's Tripodal Ligand

Cited by 23 publications

References 41 publications

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions

Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

Synthesis and structures of zirconium(IV) hydrogensulfato and carboxylato complexes with Kläui’s oxygen tripodal ligand

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