Reactivity of [Cp2Ti(CO)2] towards Nitrile and Water Adducts of B(C6F5)3: Formation of [Cp2Ti(η2‐F3CC6H4CN)·B(C6F5)3] and [Cp2Ti][HOB(C6F5)3] with a Ti···F Interaction

Choukroun, Robert; Lorber, Christian; Vendier, Laure

doi:10.1002/ejic.200300366

Cited by 23 publications

(2 citation statements)

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“…Reactivity of vanadiumoxido complexes towards B(C 6 F 5 ) 3 . [62] Scheme11. Reactivity of an uranyl(VI) complex supported by bulkyacnacligands towards B(C 6 F 5 ) 3 and reducinga gents, reported by Haytonand co-workers.…”

Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Zwettler

Mösch‐Zanetti

2019

Chemistry A European J

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Lewis acid-base pair chemistry has been placed on an ew level with the discovery that adduct formationb etween an electron donor (Lewis base) and acceptor (Lewis acid) can be inhibited by the introductiono fs teric demand, thus preserving the reactivityo fb oth Lewis centers, resulting in highly unusual chemistry.S ome of these highly versatile frustrated Lewis pairs (FLP) are capable of splitting avariety of small molecules, such as dihydrogen, in ah eterolytic and even catalytic manner.T his is in sharp contrastt oc lassical reactions where the inert substrate must be activated by am etal-basedc atalyst. Very recently,r esearch has emerged combining the two concepts,n amely the formationo fF LPs in whichametal compound represents the Lewis base, allowing for novel chemistry by using the heterolytic splitting power of both together with the redox reactivity of the metal. Such reactivity is not restricted to the metal center itself being aL ewis acid or base, also ancillary ligandsc an be used as part of the Lewis pair,s till with the benefit of the redox-active metal centern earby. This Minireview is designed to highlight the novel reactions arising from the combination of metal oxido transition-metal or rare-earthmetal compounds with the Lewis acid B(C 6 F 5 ) 3 .I tc overs a wide area of chemistry including small molecule activation, hydrogenation and hydrosilylation catalysis, and olefin metathesis, substantiating the broad influence of the novel concept. Futureg oals of this young and excitinga rea are briefly discussed.

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Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Zwettler

Mösch‐Zanetti

2019

Chemistry A European J

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“…The Lewis acid-activated nitrile was used as a reagent to facilitate η 2 :C,N interaction with the vanadocene [VCp 2 ] to give a borane adduct of vanada(IV)azirine complexes [Cp 2 V{η 2 :C,N-RCN·B(C 6 F 5 ) 3 }] (R = CH 3 , F 3 CC 6 H 4 ), for which EPR spectra provide evidence of a C−F···V intramolecular interaction. Similarly, the titanocene [Cp 2 Ti(CO) 2 ] was shown to give a borane adduct of titana(IV)azirine complex [Cp 2 Ti{η 2 :C,N-RCN·B(C 6 F 5 ) 3 }] (R = F 3 CC 6 H 4 ) …”

Section: Introductionmentioning

confidence: 78%

Mono- and Homobimetallic Vanadium Complexes: Borane Adducts of Vanada(IV)azirine Complexes

et al. 2004

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The reaction between [VCp 2 ], BPh 3 , or BCl 3 and the nitrile F 3 CC 6 H 4 CtN gives the borane adduct of vanada(IV)azirine complex [VCp 2 {η 2 :C,N-F 3 CC 6 H 4 CdN‚BR 3 }] (R ) Ph (2), Cl (3)). Using B(C 6 F 5 ) 3 and dicyano compounds such as 1,4-benzene dicarbonitrile NtC(C 6 H 4 )CtN and adiponitrile NtC(CH 2 ) 4 CtN, an access to homobimetallic vanadium complexes was obtained and complexes [(VCp 2 ) 2 {η 2 :C,N-(C 6 F 5 ) 3 B‚NdC(C 6 H 4 )CdN‚B(C 6 F 5 ) 3 }] (6) and [(VCp 2 ) 2 -{η 2 :C,N-(C 6 F 5 ) 3 B‚NdC(CH 2 ) 4 CdN‚B(C 6 F 5 ) 3 }] (8) are formed. Malononitrile NtCCH 2 CtN in the presence of 2 equiv of B(C 6 F 5 ) 3 and 1 or 2 equiv of [VCp 2 ] gave the monometallic complex [(VCp 2 ){η 2 :C,N-(C 6 F 5 ) 3 B‚NdCCH 2 CtN‚B(C 6 F 5 ) 3 }] (7). Complexes 2, 3, 7, and 8 were characterized by X-ray structure determination. All these complexes are paramagnetic to one electron per vanadium.

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The Synthesis, Structure and Reactivity of B(C₆F₅)₃‐Stabilised Amide (MNH₂) Complexes of the Group 4 Metals

Mountford

Clegg

Coles

et al. 2007

Chemistry A European J

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Treatment of the homoleptic titanium amides [Ti(NR(2))(4)] (R=Me or Et) with the Brønsted acidic reagent H(3)NB(C(6)F(5))(3) results in the elimination of one molecule of amine and the formation of the four-coordinate amidoborate complexes [Ti(NR(2))(3){NH(2)B(C(6)F(5))(3)}], the identity of which was confirmed by X-ray crystallography. The reaction with [Zr(NMe(2))(4)] proceeds similarly but with retention of the amine ligand to give the trigonal-bipyramidal complex [Zr(NMe(2))(3){NH(2)B(C(6)F(5))(3)}(NMe(2)H)]. Cyclopentadienyl (Cp) amidoborate complexes, [MCp(NR(2))(2){NH(2)B(C(6)F(5))(3)}] (M=Ti, R=Me or Et; M=Zr, R=Me) can be prepared from [MCp(NR(2))(3)] and H(3)NB(C(6)F(5))(3), and exhibit greater thermal stability than the cyclopentadienyl-free compounds. H(3)NB(C(6)F(5))(3) reacts with nBuLi or LiN(SiMe(3))(2) to give LiNH(2)B(C(6)F(5))(3), which complexes with strong Lewis acids to form ion pairs that contain weakly coordinating anions. The attempted synthesis of metallocene amidoborate complexes from dialkyl or diamide precursors and H(3)NB(C(6)F(5))(3) was unsuccessful. However, LiNH(2)B(C(6)F(5))(3) does react with the highly electrophilic reagents [MCp(2)Me(mu-Me)B(C(6)F(5))(3)] to give [MCp(2)Me(mu-NH(2))B(C(6)F(5))(3)] (M=Zr or Hf). Comparison of the molecular structures of the Group 4 amidoborate complexes reveals very similar B--N, Ti--N and Zr--N bond lengths, which are consistent with a description of the bonding as a dative interaction between an {M(L)(n)(NH(2))} fragment and the Lewis acid B(C(6)F(5))(3). Each of the structures has an intramolecular hydrogen-bonding arrangement in which one of the nitrogen-bonded hydrogen atoms participates in a bifurcated FHF interaction to ortho-F atoms.

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Reactivity of [Cp₂Ti(CO)₂] towards Nitrile and Water Adducts of B(C₆F₅)₃: Formation of [Cp₂Ti(η²‐F₃CC₆H₄CN)·B(C₆F₅)₃] and [Cp₂Ti][HOB(C₆F₅)₃] with a Ti···F Interaction

Cited by 23 publications

References 35 publications

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Mono- and Homobimetallic Vanadium Complexes: Borane Adducts of Vanada(IV)azirine Complexes

The Synthesis, Structure and Reactivity of B(C₆F₅)₃‐Stabilised Amide (MNH₂) Complexes of the Group 4 Metals

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Reactivity of [Cp2Ti(CO)2] towards Nitrile and Water Adducts of B(C6F5)3: Formation of [Cp2Ti(η2‐F3CC6H4CN)·B(C6F5)3] and [Cp2Ti][HOB(C6F5)3] with a Ti···F Interaction

Cited by 23 publications

References 35 publications

Interaction of Metal Oxido Compounds with B(C6F5)3

Interaction of Metal Oxido Compounds with B(C6F5)3

Mono- and Homobimetallic Vanadium Complexes: Borane Adducts of Vanada(IV)azirine Complexes

The Synthesis, Structure and Reactivity of B(C6F5)3‐Stabilised Amide (MNH2) Complexes of the Group 4 Metals

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Reactivity of [Cp₂Ti(CO)₂] towards Nitrile and Water Adducts of B(C₆F₅)₃: Formation of [Cp₂Ti(η²‐F₃CC₆H₄CN)·B(C₆F₅)₃] and [Cp₂Ti][HOB(C₆F₅)₃] with a Ti···F Interaction

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

The Synthesis, Structure and Reactivity of B(C₆F₅)₃‐Stabilised Amide (MNH₂) Complexes of the Group 4 Metals