New Examples of Half-Sandwich (Borylcyclopentadienyl)titanium Trichloride Complexes and an X-ray Structural Characterization of the Homobimetallic Complex [TiCl3{η5-C5H4}]2BPh

Larkin, Scott A.; Golden, Jeffery T.; Shapiro, Pamela J.; Yap, Glenn P. A.; Foo, and David Ming Jin; Rheingold, Arnold L.

doi:10.1021/om9600699

Cited by 52 publications

(33 citation statements)

References 39 publications

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“…The bite angles of the base‐free amidoborylidene‐bridged species, complexes II , XI , and XII , are quite narrow for sp 2 ‐hybridized boron atoms (cf. the 127° bridge angle for the bimetallic titanium complex II shown in Scheme 39), illustrating the considerable strain experienced by an sp 2 ‐hybridized boron atom in the ansa position.…”

Section: Introductionmentioning

confidence: 97%

Boron-Bridged Group-4ansa-Metallocene Complexes

Shapiro

2001

Eur. J. Inorg. Chem.

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Boron‐bridged group‐4 ansa‐metallocene complexes are newcomers to the field of metallocene‐mediated olefin polymerization catalysis. Because of the Lewis acidity of the boron bridge, it is more reactive than the more common carbon and silicon bridges. It is also more vulnerable to cleavage from the ligand framework by nucleophilic agents. A primary goal of our work is to involve the boron bridge more actively in the reaction chemistry of the metallocene while keeping the bridge intact.

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Section: Introductionmentioning

confidence: 97%

Boron-Bridged Group-4ansa-Metallocene Complexes

Shapiro

2001

Eur. J. Inorg. Chem.

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“…Li; b) [Zr(CH 2 Ph) 4 ].that the reaction of neutral bis[(trimethylsilyl)cyclopentadienyl]phenyl borane(14) with TiCl 4 gives a binuclear complex with loss of Me 3 SiCl (Scheme 13) [23]. Scheme 13.…”

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confidence: 99%

Zwitterionic Metallocenes

Piers

1998

Chem. Eur. J.

116

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Ion pairing in cationic metallocenes capable of the polymerization of olefins affects the activity of these catalysts. One strategy for minimizing ion ± ion contacts is the preparation of zwitterionic analogues of the catalysts in which the counterion is affixed covalently to the ancillary or reactive ligand structure of the molecule. The concepts behind the varied synthetic approaches taken to three families of zwitterionic metallocenes, classified by the location of the counterion in the molecular structure, are discussed.

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“…Despite a number of attempts to optimize this reaction (at lower temperatures and with variable equivalents of BF 3 ·Et 2 O), 2 could not be obtained in an analytically pure state, with 1 being a persistent and inseparable impurity. A number of other examples of multiple metal-Cp fragments being linked together through a neutral borane moiety have been reported in the literature. − …”

Section: Resultsmentioning

confidence: 99%

Electronic Structures of Rhenium(II) β-Diketiminates Probed by EPR Spectroscopy: Direct Comparison of an Acceptor-Free Complex to Its Dinitrogen, Isocyanide, and Carbon Monoxide Adducts

et al. 2020

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Electron paramagnetic resonance (EPR) studies of the rhenium(II) complex Re(η 5 -Cp)(BDI) (1; BDI = N,N′bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) have revealed that this species reversibly binds N 2 in solution: flash frozen toluene solutions of 1 disclose entirely different EPR spectra at 10 K when prepared under N 2 versus Ar atmospheres. This observation was additionally verified by the synthesis of stable CO and 2,6-xylylisocyanide (XylNC) adducts of 1, which display EPR features akin to those observed in the putative N 2 complex. While we found that 1 displays an extremely large g max value of 3.99, the binding of an additional ligand leads to substantial decreases in this value, displaying g max values of ca. 2.4. Following the generation of isotopically enriched 15 N 2 and 13 CO adducts of 1, HYSCORE experiments allowed for the measurement of the corresponding hyperfine couplings associated with spin delocalization onto the electron-accepting ligands in these species, which proved to be small. A cumulative assessment of the EPR data, when combined with insights provided by near-infrared (NIR) spectroscopy and time-dependent density functional theory (TDDFT) calculations, indicated that while the binding of electron acceptors to 1 does lead to decreases in g max in relative accord with the field strength (i.e., π-acidity) of the variable ligand, the magnitude of these decreases is primarily due to the changes in electronic structure at the Re center.

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New Examples of Half-Sandwich (Borylcyclopentadienyl)titanium Trichloride Complexes and an X-ray Structural Characterization of the Homobimetallic Complex [TiCl₃{η⁵-C₅H₄}]₂BPh

Cited by 52 publications

References 39 publications

Boron-Bridged Group-4ansa-Metallocene Complexes

Boron-Bridged Group-4ansa-Metallocene Complexes

Zwitterionic Metallocenes

Electronic Structures of Rhenium(II) β-Diketiminates Probed by EPR Spectroscopy: Direct Comparison of an Acceptor-Free Complex to Its Dinitrogen, Isocyanide, and Carbon Monoxide Adducts

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