Cyclic organohydroborate complexes of metallocenes

Lacroix, Fabrice; Plečnik, Christine E.; Liu, Shengming; Liu, Fuchen; Meyers, Edward A.; Shore, Sheldon G.

doi:10.1016/j.jorganchem.2003.08.010

Cited by 16 publications

(26 citation statements)

References 41 publications

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“…In spite of the excess of H 3 B·THF, the final products are neither Zr(BH 4 ) 4 nor [(BuO) n Zr(BH 4 ) 4-n ]·THF. Equations (1) to (4) describe the formation of compounds 4 to 6. In spite of the enrichment of the [BuOZr(BH 4 ) 3 ] species, no single crystals could be isolated.…”

Section: Resultsmentioning

confidence: 99%

“…In spite of the enrichment of the [BuOZr(BH 4 ) 3 ] species, no single crystals could be isolated. This may be due to the fact that compounds Zr(BH 4 ) 4 or Zr(BH 4 ) 4 ·(THF) n are not formed because their precursor 6 is most likely not monomeric.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast to the unknown titanium(IV) tetrahydroborate, the element homologous zirconium and hafnium compounds M(BH 4 ) 4 show a marked increase in thermal stability and resist reduction even at moderately increased temperatures. [1] On the other hand, [Ti(BH 4 ) 3 ] 2 is sufficiently stable and its structure is well known.…”

Section: Introductionmentioning

confidence: 97%

“…[3] The higher stability of the Zr and Hf compounds against reduction is due to the fact that they have a filled 3d shell in the case of Zr and completely filled 4d and 4f shells in the case of Hf. Therefore, the chemistry of Zr and Hf hydridoborates and their derivatives are much better developed [1,4] than that of the corresponding Ti III hydridoborates. [5] Typical examples are compounds 1 and 2, as shown by G. S. Girolami et al [6] The high stability of zirconium tetrahydridoborates should allow their synthesis from Zr(OR) 4 compounds and H 3 B·THF.…”

Section: Introductionmentioning

confidence: 99%

“…The most stable zirconium hydridoborates contain zirconocene units. [7] They can be obtained from Cp 2 ZrCl 2 and LiBH 4 or LiH 4-n BR n compounds.…”

Section: Introductionmentioning

confidence: 99%

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Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

2011

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The reactions of Zr(OBu)4 and Zr(OEt)4 with H3B·THF in THF led to HB(OR)2 and B(OR)3, but no zirconium tetrahydroborate [(RO)4–nZr(BH4)n] could be isolated. On the contrary, the reactions of [tBu3CO]4–nZrCln and [tBu3SiO]4–nZrCln with LiBH4 generated the tetrahydroborates [(RO)3Zr(BH4)] and [(RO)2Zr(BH4)2]. These can be used to produce by hydroborate exchange dihydridodiorganyl borates [(RO)4–nZr(H2BC8H14)n] and byproducts. The structures of the new zirconium hydridoborates have been determined by X‐ray crystallography. Compound [(tBu3CO)3Zr(H2BC8H14)] shows site‐disordered dihydroborate units with agostic Zr–H–C interactions, while [(tBu3SiO)2Zr(H2BC8H14)2] is quite symmetric (C2/c). The corresponding tetrahydridoborates possess in most cases μ31‐bonded ZrH3BH groups.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

“…The most stable zirconium hydridoborates contain zirconocene units. [7] They can be obtained from Cp 2 ZrCl 2 and LiBH 4 or LiH 4-n BR n compounds.…”

Section: Introductionmentioning

confidence: 99%

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Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

2011

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Ring‐Opening Reactions of Epoxides With Titanium(III) Reagents

RajanBabu¹,

Nugent²,

Halder³

2022

Organic Reactions

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The ring‐opening reactions of epoxides with titanium(III) reagents such as Cp 2 TiCl are critically reviewed, including the scope, limitations, and mechanism of these synthetically useful transformations. The initial reaction proceeds by single‐electron transfer to give a carbon‐centered β‐titanoxy radical. The resulting radical can be terminated by a number of different reaction pathways, including epoxide deoxygenation, reduction to the alcohol, intermolecular addition to activated olefins, and intramolecular addition (cyclization). The literature is surveyed from the first reported examples in 1988 through October, 2021.

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The Structure of Potassium and Tetramethylammonium Salts of the Cyclic Organohydroborate Anion [H₂BC₈H₁₄]^– with Different Solvent Ligands

Chen

Liu

et al. 2007

Eur J Inorg Chem

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Solvated potassium salts of the 9‐BBN hydroborate anion have been prepared and their structures have been determined by single‐crystal X‐ray diffraction analyses. A tetrameric complex {LK[(μ‐H)2BC8H14]}4 is formed when L is toluene, MeTHF, toluene/THF, THF/Et2O mixtures. The basic framework consists of a distorted K4B4 cube in which potassium and boron are at alternate corners of the cube linked by bridging hydrogen atoms and α‐C–H hydrogen atoms from the 9‐BBN hydroborate that appear to form agostic interactions with potassium. There are two types of bridging hydrogen atoms: one is connected to three potassium atoms and one boron atom in a μ4‐coordination arrangement, and the other one is connected to two potassium atoms and one boron atom in a μ3‐coordination arrangement. There are four μ4‐hydrogen arrangements in the structure. They are located inside of the K4B4 cube. The four μ3‐hydrogen arrangements are located outside of the distorted K4B4 cube. The coordination number of potassium is 8 with the three μ4‐, two μ3‐bridging hydrogen atoms, two α‐C–H hydrogen atoms, and one oxygen atom of the solvent, L (there is a weak π‐η6 interaction when the solvent is toluene). On the other hand, in the chelating solvent DME, a dimeric structure is formed in which the inner part is planar with potassium and boron located at alternate corners. The potassium is connected to four μ3‐bridging hydrogen atoms, two apparent agostic α‐C–H bonding hydrogen atoms, and four oxygen atoms of two DME molecules. Its coordination number is 10 including the agostic interactions. The structure of the uncoordinated [H2BC8H14]– anion is observed in the tetramethylammonium salt. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Cyclic organohydroborate complexes of metallocenes

Cited by 16 publications

References 41 publications

Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

Ring‐Opening Reactions of Epoxides With Titanium(III) Reagents

The Structure of Potassium and Tetramethylammonium Salts of the Cyclic Organohydroborate Anion [H₂BC₈H₁₄]^– with Different Solvent Ligands

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Cyclic organohydroborate complexes of metallocenes

Cited by 16 publications

References 41 publications

Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

Triorganyl‐ and Diorganyloxozirconium Hydridoborates – Synthesis and Structures

Ring‐Opening Reactions of Epoxides With Titanium(III) Reagents

The Structure of Potassium and Tetramethylammonium Salts of the Cyclic Organohydroborate Anion [H2BC8H14]– with Different Solvent Ligands

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The Structure of Potassium and Tetramethylammonium Salts of the Cyclic Organohydroborate Anion [H₂BC₈H₁₄]^– with Different Solvent Ligands