Organometallic Halides:  Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C5Me5)V(μ-Cl)2]3

Abernethy, Colin D.; Bottomley, Frank; Decken, Andreas; Thompson, Robert C.

doi:10.1021/om960482g

Cited by 29 publications

(31 citation statements)

References 57 publications

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“…The titanium–titanium distance in 3 of 3.219(1) Å is slightly shorter than that found in the dimer 2 . Analogous cyclic trinuclear structures have been structurally documented for complexes [{Zr(η 5 -1,2,4-( t Bu) 3 C 5 H 2 )(μ-Cl) 2 } 3 ] and [{V(η 5 -C 5 Me 4 R)(μ-Cl) 2 } 3 ] (R = Me, Et) …”

Section: Resultsmentioning

confidence: 85%

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

et al. 2019

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Following the track of the useful titanocene [Ti( 5 -C5H5)2Cl] reagent in organic synthesis, the related half-sandwich titanium(III) derivatives [Ti( 5 -C5R5)Cl2] are receiving increasing attention in radical chemistry of many catalyzed transformations. However, the structure of the active titanium(III) species remains unknown in the literature. Herein, we describe the synthesis, crystal structure, and electronic structure of titanium( III) aggregates of composition [{Ti( 5 -C5Me5)Cl2}n]. The thermolysis of [Ti( 5 -C5Me5)Cl2Me] (1) in benzene or hexane at 180 ºC results in the clean formation of [{Ti( 5 -C5Me5)Cl(-Cl)}2] (2), methane and ethene. The treatment of 1 with excess pinacolborane in hexane at 65 ºC leads to a mixture of 2 and the paramagnetic trimer [{Ti( 5 -C5Me5)(-Cl)2}3] (3). The Xray crystal structures of compounds 2 and 3 show Ti-Ti distances of 3.267(1) and 3.219(12) Å, respectively. Computational studies (CASPT2//CASSCF and BS DFT methods) for dimer 2 reveal a singlet ground state and a relatively large singlet-triplet energy gap. Nuclear magnetic resonance (NMR) spectroscopy of 2 in aromatic hydrocarbon solutions and DFT calculations for several [{Ti( 5 -C5Me5)Cl2}n] aggregates are consistent with the existence of an equilibrium between the diamagnetic dimer [{Ti( 5 -C5Me5)Cl(-Cl)}2] and a paramagnetic tetramer [{Ti( 5 -C5Me5)(-Cl)2}4] in solution. In contrast, complex 2 readily dissolves in tetrahydrofuran to give a green-blue solution from which blue crystals of the mononuclear adduct [Ti( 5 -C5Me5)Cl2(thf)] (4) were grown.

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Section: Resultsmentioning

confidence: 85%

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

et al. 2019

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“…[LiBH 4 ·THF], [BH 3 ·THF], CCl 4 , and Ph 2 Se 2 (Aldrich) were used as purchased. The compounds (Cp*VCl 2 ) 3 and [Bu 4 N(B 3 H 8 )], as references for 11 B{ 1 H} NMR spectra, were prepared following the literature methods. Thin-layer chromatography was carried out on silica-gel TLC plates supported by dialuminum (Merck).…”

Section: Methodsmentioning

confidence: 99%

B–H Functionalization of Hydrogen-Rich [(CpV)₂(B₂H₆)₂]: Synthesis and Structures of [(CpV)₂(B₂X₂)₂H₈] (X = Cl, SePh; Cp* = η⁵-C₅Me₅)

et al. 2019

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We have recently reported the perchlorinated diniobaborane species [(Cp*Nb)2(B2H4Cl2)2] from [(Cp*Nb)2(B2H6)2] using CCl4 as chlorinating agent. In an attempt to isolate the vanadium analogue, we have isolated [(Cp*V)2(B2H6)2], 1 from the reaction of (Cp*VCl2)3 with [LiBH4•THF] followed by thermolysis with excess [BH3•THF]. Subsequently, the thermolysis of 1 with CCl4 for a prolonged period of time afforded perchlorinated divanadaborane [(Cp*V)2(B2H4Cl2)2], 2 along with the formation of bichlorinated divanadaborane [(Cp*V)2(B2H5Cl)2], 3 and trichlorinated divanadaborane [(Cp*V)2(B2H4Cl2)(B2H5Cl)], 4. Similarly, in order to functionalize the terminal B-H by {SePh} group, thermolysis of 1 was carried out with Ph2Se2 that yielded persubstituted divanadaborane [(Cp*V)2{B2H4(SePh)2}2], 5 in parallel to the formation of [(Cp*V)2{B4H11(SePh)}], 6. Compound 5 is very fascinating in which all the terminal B-H hydrogens of 1 have been substituted by {SePh} ligands. All the compounds have been characterized by 1 H, 11 B, 13 C NMR spectroscopy; mass spectrometry; IR spectroscopy and single crystal X-ray analysis. Density functional theory (DFT) and TD-DFT calculations provided further understanding regarding the electronic structures, bonding and electronic transitions of these persubstituted vanadaborane species.

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“…31 Other high-yield routes to 17a have recently been explored. 32,33 Its half-sandwich structure has been confirmed. 24 An equilibrium exists between the mononuclear 17a and the oxo-bridged dinuclear complex, [Cp*V(O)Cl] 2 ("-O) (18a), depending on the availability of chloro and oxo ligands (Scheme 8).…”

Section: Compounds Containing Vanadium(v)mentioning

confidence: 76%

Sandwich and half-sandwich complexes derived from pentamethylcyclopentadienyl tetracarbonyl vanadium, Cp*V(CO)4

Herberhold

Dietel

Peukert

et al. 2000

Appl. Organometal. Chem.

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Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C₅Me₅)V(μ-Cl)₂]₃

Cited by 29 publications

References 57 publications

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

B–H Functionalization of Hydrogen-Rich [(CpV)₂(B₂H₆)₂]: Synthesis and Structures of [(CpV)₂(B₂X₂)₂H₈] (X = Cl, SePh; Cp* = η⁵-C₅Me₅)

Sandwich and half-sandwich complexes derived from pentamethylcyclopentadienyl tetracarbonyl vanadium, Cp*V(CO)4

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Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C5Me5)V(μ-Cl)2]3

Cited by 29 publications

References 57 publications

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

The Puzzling Monopentamethylcyclopentadienyltitanium(III) Dichloride Reagent: Structure and Properties

B–H Functionalization of Hydrogen-Rich [(Cp*V)2(B2H6)2]: Synthesis and Structures of [(Cp*V)2(B2X2)2H8] (X = Cl, SePh; Cp* = η5-C5Me5)

Sandwich and half-sandwich complexes derived from pentamethylcyclopentadienyl tetracarbonyl vanadium, Cp*V(CO)4

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Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C₅Me₅)V(μ-Cl)₂]₃

B–H Functionalization of Hydrogen-Rich [(CpV)₂(B₂H₆)₂]: Synthesis and Structures of [(CpV)₂(B₂X₂)₂H₈] (X = Cl, SePh; Cp* = η⁵-C₅Me₅)