Investigation of the Reactivity of Hydroxyborate Salts with Group IV Metal Complexes: Synthesis and Structural Characterization of the Zirconium and Hafnium Ionic Complexes [PPN]+[Cp2MMe(OB(C6F5)3)]−

Kelsen, Vinciane; Vallée, Christophe; Jeanneau, Erwann; Bibal, Christine; Santini, Catherine C.; Chauvin, Yves; Olivier‐Bourbigou, Hélène

doi:10.1021/om2002798

Cited by 12 publications

(13 citation statements)

References 47 publications

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“…Both zirconium compounds containing a Zr=O−B moiety remain tetrahedral, realized by an additional Zr−F interaction in the former and a methyl group in the latter (Figure ). More recently, similar reactivity was also found for related hafnocene compounds …”

Section: Non‐conventional Metal Oxido Borane Adduct Formationsupporting

confidence: 79%

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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: Non‐conventional Metal Oxido Borane Adduct Formationsupporting

confidence: 79%

“…More recently,s imilarr eactivity was also found for related hafnocenecompounds. [50] Figure 2. Selectedexamples of transition metal oxido-based Lewis adducts synthesized by Green and co-workers.…”

Section: Non-conventional Metal Oxido Borane Adduct Formationmentioning

confidence: 99%

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Zwettler

Mösch‐Zanetti

2019

Chemistry A European J

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“…BPh 3 does however still possess sufficient hydridophilicity to be useful as a catalyst in FLP‐type reactions as recently demonstrated . While H 2 O–B(C 6 F 5 ) 3 is well documented, the corresponding H 2 O–BPh 3 adduct is less studied, particularly its ability to act as a Brønsted acid . Herein we report an extension to the water and base tolerance of boranes to strong amine bases, focusing, in particular on the triarylborane‐catalysed reductive amination of aldehydes/ketones with alkylamines using silanes as reducing agents.…”

Section: Introductionmentioning

confidence: 98%

Expanding Water/Base Tolerant Frustrated Lewis Pair Chemistry to Alkylamines Enables Broad Scope Reductive Aminations

Fasano

Ingleson

2017

Chemistry A European J

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Lower Lewis acidity boranes demonstrate greater tolerance to combinations of water/strong Brønsted bases than B(C6F5)3, this enables Si−H bond activation by a frustrated Lewis pair (FLP) mechanism to proceed in the presence of H2O/alkylamines. Specifically, BPh3 has improved water tolerance in the presence of alkylamines as the Brønsted acidic adduct H2O–BPh3 does not undergo irreversible deprotonation with aliphatic amines in contrast to H2O–B(C6F5)3. Therefore BPh3 is a catalyst for the reductive amination of aldehydes and ketones with alkylamines using silanes as reductants. A range of amines inaccessible using B(C6F5)3 as catalyst, were accessible by reductive amination catalysed by BPh3 via an operationally simple methodology requiring no purification of BPh3 or reagents/solvent. BPh3 has a complementary reductive amination scope to B(C6F5)3 with the former not an effective catalyst for the reductive amination of arylamines, while the latter is not an effective catalyst for the reductive amination of alkylamines. This disparity is due to the different pK a values of the water–borane adducts and the greater susceptibility of BPh3 species towards protodeboronation. An understanding of the deactivation processes occurring using B(C6F5)3 and BPh3 as reductive amination catalysts led to the identification of a third triarylborane, B(3,5‐Cl2C6H3)3, that has a broader substrate scope being able to catalyse the reductive amination of both aryl and alkyl amines with carbonyls.

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“…AQESIZ (Mukherjee et al, 2011); AXIBOA (Boulho et al2016); BESGOW (Bolig & Chen, 2004); BODMIR (Helmstedt et al, 2008); BUHVAD (Xu et al, 2015); BUYSOD10 (Longato et al, 1985); CADRUU (Hunter et al, 1983); COHTEY (Waymouth et al, 1984); COPRII (Ho et al, 1984); DAGKAX and DAGKIF (Gambarotta et al, 1985); DITHAP (Martin et al, 1985); EHEFUT (Neu et al, 2011); EKEVEX, EKEVIB, EKEVOH, EKEVUN, EKEWAU and EKEWEY (Normand et al, 2016); ESISAA (Zuccaccia et al, 2004); GIPYUZ (Matchett et al, 1988); HEMCOR (Askham et al, 1994); HIKHUF and HIKJAN (Gurubasavaraj et al, 2007); HUVLAL (Fujdala et al, 2003); IGUDOD (Hü erlä nder et al, 2002); JITVAK and JITVEO (Mandal et al, 2007); JUGCIZ (Boulho et al, 2015); KEXYER (Erker et al, 1990); KODQAV (Koch et al, 2000); KUPQAP (Mariott & Chen, 2005); LEDBEB (Askham et al, 1993); LEPXAH (Mukherjee et al, 2013); MOJHEZ (Black et al, 2008); NAHYOL (Bai et al, 2005); NAPXUY (Pineda et al, 2005); NIMNOM (Johnson et al, 1997); ODOBIU, ODOBOA and ODOBUG (Frö mel et al, 2013); OKUFUX (Bestgen et al, 2016); OZUCAO (Kelsen et al, 2011); PEDFUA (Singh et al, 2006); QIZCEI ; REDTUQ (Cummings et al, 2006); TIWKUG (Yang, Schulz et al, 2008); TOWMUN (Breen & Stephan, 1996); VIBSOO (Waymouth et al, 1990); WAJLO...…”

Section: Figurementioning

confidence: 99%