Synthesis and Structure of the Dimethyl Sulfide Adducts of Mono- and Bis(pentafluorophenyl)borane

Fuller, A. T.; Hughes, David L.; Lancaster, Simon; White, Callum M.

doi:10.1021/om100152v

Cited by 43 publications

(37 citation statements)

References 18 publications

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“…Dihydrogen was purchased from BOC in 99.995 % purity and used as received. IrH 2 POCOP [75] and HB(C 6 F 5 ) 2 ·SMe 2 [89] were synthesised via literature methods. B(C 6 F 5 ) 3 was synthesised via the method of Lancaster and co-workers and sublimed at 100°C at 2 ϫ 10 -2 mbar prior to use.…”

Section: Methodsmentioning

confidence: 99%

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake

et al. 2011

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The amine-borane adduct iPr 2 NH·BH(C 6 F 5 ) 2 (1) and the aminoborane iPr 2 N=B(C 6 F 5 ) 2 (2) have been prepared and crystallographically characterised. Interconversion between the two compounds has been attempted using thermal and transition-metal-catalysed dehydrogenation and hydrogenation protocols and the overall reaction thermodynamics were probed by computational methods. Thermal dehydrogenation of 1 was found to yield 2, together with uncharacterised by-products. Treatment of 1 with the carbene 1,3-di-tert-butyl-4,5-dihydroimidazol-2-ylidene (3) under ambient conditions did not lead to the elimination of hydrogen, but instead

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Section: Methodsmentioning

confidence: 99%

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake

et al. 2011

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“…We recently developed a convenient synthesis of the mono-and bis(pentafluorophenyl)borane adducts of dimethylsulfide. [22] These precursors have facilitated the synthetic and structural investigation of the chemistry of Li, Zr and Hf complexes of the [NH 2 BA C H T U N G T R E N N U N G (C 6 F 5 ) 2 H] À and [NH 2 B-A C H T U N G T R E N N U N G (C 6 F 5 )H 2 ] À ligands, with both BÀH and NÀH functions reported herein. In the metallocene compounds, agostic M···H À B interactions are a prominent feature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Amido‐ and Imido(pentafluorophenyl)borane Zirconocene and Hafnocene Complexes: NH and BH Activation

Jacobs

Fuller

Coles

et al. 2012

Chemistry A European J

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Treatment of Me(2)S·B(C(6)F(5))(n) H(3-n) (n=1 or 2) with ammonia yields the corresponding adducts. H(3)N·B(C(6)F(5))H(2) dimerises in the solid state through N-H···H-B dihydrogen interactions. The adducts can be deprotonated to give lithium amidoboranes Li[NH(2)B(C(6)F(5))(n)H(3-n)]. Reaction of the n=2 reagent with [Cp(2)ZrCl(2)] leads to disubstitution, but [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)] is in equilibrium with the product of β-hydride elimination [Cp(2)Zr(H){NH(2)B(C(6)F(5))(2)H}], which proves to be the major isolated solid. The analogous reaction with [Cp(2)HfCl(2)] gives a mixture of [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)] and the N-H activation product [Cp(2)Hf{NHB(C(6)F(5 )(2)H}]. [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)]·PhMe and [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]·4(thf) exhibit β-B-agostic chelate bonding of one of the two amidoborane ligands in the solid state. The agostic hydride is invariably coordinated to the outside of the metallocene wedge. Exceptionally, [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]⋅PhMe has a structure in which the two amidoborane ligands adopt an intermediate coordination mode, in which neither is definitively agostic. [Cp(2)Hf{NHB(C(6)F(5))(2)H}] has a formally dianionic imidoborane ligand chelating through an agostic interaction, but the bond-length distribution suggests a contribution from a zwitterionic amidoborane resonance structure. Treatment of the zwitterions [Cp(2)MMe(μ-Me)B(C(6)F(5))(3)] (M=Zr, Hf) with Li[NH(2)B(C(6)F(5))(n)H(3-n)] (n=2) results in [Cp(2) MMe{NH(2)B(C(6)F(5))(2)H}] complexes, for which the spectroscopic data, particularly (1)J(B,H), again suggest β-B-agostic interactions. The reactions proceed similarly for the structurally encumbered [Cp''(2)ZrMe(μ-Me)B(C(6)F(5))(3)] precursor (Cp''=1,3-C(5)H(3)(SiMe(3))(2) , n=1 or 2) to give [Cp''(2)ZrMe{NH(2)B(C(6)F(5))(n)H(3-n)}], both of which have been structurally characterised and show chelating, agostic amidoborane coordination. In contrast, the analogous hafnium chemistry leads to the recovery of [Cp''(2)HfMe(2)] and the formation of Li[HB(C(6)F(5))(3)] through hydride abstraction.

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“…directly with "Lancaster's reagent" [H 2 B(C 6 F 5 )]·SMe 2 [16] (2 h, r.t., [ D 8 ]toluene). The NMR analysis showedt he formation of the FLP 11 a plus Me 2 S. We also performed both these reactions (paths {A} and {B}, see Scheme 3) with the Br Eind-substituted startingm aterials 7b and 4b,r espectively.I nb oth cases, this resultedi napracticallyq uantitative conversion to the Br Eind-substituted FLP system 11 b (X: Br;s ee the SupportingI nformation for the spectroscopic characterization).…”

Section: Formation Of the Cyclic Five-membered (Br)-eind-substituted mentioning

confidence: 99%

Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

Dong

Daniliuc

Kehr

et al. 2019

Chemistry A European J

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The cyclic five-membered frustratedp hosphane/ borane Lewis pairs 11 a, b featuring the bulky octaethylhydrindacenyl-(Eind) substituento ri ts mono-bromod erivative ( Br Eind)a tp hosphorus are monomeric at room temperature. The reactive frustrated Lewis pairs (FLPs) cleave dihydrogen. The cyclic FLP 11 b ( Br Eind) undergoes 1,2-P/B addition to ethylene to give the zwitterionic heteronorbornane derivative 14 b.I tr eacts similarly with the carbon-carbon double bond of norbornene.W ith av ariety of organic p-reagents, the cyclic FLP 11 b often undergoes reaction sequences reminiscent of the Alder-Rickert reaction:the cycloaddition reaction is followed by rapid cycloreversion to form new fivemembered heterocyclic FLP products with extrusion of ethene. Reactions of 11 b with benzaldehydeo rw ith acetylenesf ollow this reactionpattern.Scheme1.Previously reported P/B cyclo-FLPs and the bulkyaryl ligands used in this study.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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Synthesis and Structure of the Dimethyl Sulfide Adducts of Mono- and Bis(pentafluorophenyl)borane

Cited by 43 publications

References 18 publications

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake

Synthesis and Structure of Amido‐ and Imido(pentafluorophenyl)borane Zirconocene and Hafnocene Complexes: NH and BH Activation

Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

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Synthesis and Structure of the Dimethyl Sulfide Adducts of Mono- and Bis(pentafluorophenyl)borane

Cited by 43 publications

References 18 publications

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr2NH·BH(C6F5)2 and the Aminoborane iPr2N=B(C6F5)2 Involving Hydrogen Loss and Uptake

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr2NH·BH(C6F5)2 and the Aminoborane iPr2N=B(C6F5)2 Involving Hydrogen Loss and Uptake

Synthesis and Structure of Amido‐ and Imido(pentafluorophenyl)borane Zirconocene and Hafnocene Complexes: NH and BH Activation

Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions

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Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake

Experimental and Theoretical Studies of the Potential Interconversion of the Amine–Borane iPr₂NH·BH(C₆F₅)₂ and the Aminoborane iPr₂N=B(C₆F₅)₂ Involving Hydrogen Loss and Uptake