Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

Osipova, Elena S.; Gulyaeva, Ekaterina S.; Gutsul, Evgenii I.; Kirkina, Vladislava A.; Pavlov, Alexander A.; Nelyubina, Yulia V.; Rossin, Andrea; Peruzzini, Maurizio; Epstein, Lina M.; Belkova, Natalia V.; Filippov, Oleg A.; Shubina, Elena S.

doi:10.1039/d0sc06114j

Cited by 15 publications

(11 citation statements)

References 59 publications

(46 reference statements)

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“…Since then, the corresponding reactivity of other FLPs including geminal intramolecular FLPs, Zr/P based FLP systems, and the xanthene-based intramolecular FLP C 13 H 6 Me 2 O(PMes 2 )(B(C 6 F 5 ) 2 ) have been used in both stoichiometric and catalytic dehydrogenations of amine-borane adducts (Scheme ). Most recently, the fully metal-based FLP derived from the combination of the basic [C 6 H 4 (2,6-(CH 2 P t -Bu 2 ) 2 )PdH] and the acidic CpWH(CO) 3 was used to catalytically liberate H 2 via the dehydrogenation of the Me 2 NHBH 3 or t -BuNH 2 BH 3 …”

Section: Flp Reductionsmentioning

confidence: 99%

Diverse Uses of the Reaction of Frustrated Lewis Pair (FLP) with Hydrogen

Stephan

2021

J. Am. Chem. Soc.

139

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The articulation of the notion of “frustrated Lewis pairs” (FLPs) emerged from the discovery that H2 can be reversibly activated by combinations of sterically encumbered main group Lewis acids and bases. This has prompted numerous studies focused on various perturbations of the Lewis acid/base combinations and the applications to organic reductions. This Perspective focuses on the new directions and developments that are emerging from this FLP chemistry involving hydrogen. Three areas are discussed including new applications and approaches to FLP reductions, the reductions of small molecules, and the advances in heterogeneous FLP systems. These foci serve to illustrate that despite having its roots in main group chemistry, this simple concept of FLPs is being applied across the discipline.

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Section: Flp Reductionsmentioning

confidence: 99%

Diverse Uses of the Reaction of Frustrated Lewis Pair (FLP) with Hydrogen

Stephan

2021

J. Am. Chem. Soc.

139

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“…Another recent example of amine-borane dehydrogenation utilises a bimetallic frustrated Lewis pair (FLP) system which bears a Lewis acidic Pd site and a Lewis basic W site, reminiscent of MLC strategies (Scheme 25). 71 The two FLP components [Pd(PCP)] + and [W(CO) [Pd(PCP)] + , [WH(CO) 3 L] and [W(CO) 3 L] À in isolation showed no activity in dehydrogenation, suggesting the necessity of both metal centres for catalytic activity.…”

Section: Amine-borane Dehydrogenationmentioning

confidence: 99%

Cooperative approaches in catalytic hydrogenation and dehydrogenation

Stevens

Colebatch

2022

Chem. Soc. Rev.

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“…As hinted, the most common synthetic procedure for the preparation of mono-aminoboranes would involve dehydrogenation and/or dehydrocoupling of amine-boranes under heating or catalytic reaction conditions (Scheme a). − ,− The overall dehydrogenation is also possible via a two-step procedure involving initial activation of either a hydridic B–H , or a protic N–H bond followed by an N–H or a B–H bond cleavage, respectively. On the other hand, the preparation of bis-aminoboranes has been significantly less exploited compared to their mono-amino analogues.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Mono- and Acyclic Bis-aminoboranes via Controlled Hydroboration of Imines

et al. 2022

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Controlled hydroboration of imines using Me2S-BH3 has been developed as an alternative approach toward the synthesis of both mono- and acyclic bis-aminoboranes. One of the key synthetic steps involved isolation of the imine-BH3 adducts followed by their conversion to the corresponding mono-aminoboranes (R2N-BH2; R = alkyl, aryl). This particular transformation could be achieved thermally, but the best results in terms of product purities were obtained in the presence of catalytic amounts of a β-diketiminate stabilized aluminum complex (i.e., LAl(OTf)2/Na[BArCl 4]; Tf = O2SCF3, L = CH(CCH3)2(N(2,6-iPr2-C6H3))2, ArCl = 3,5-Cl2-C6H3). Symmetrical bis-aminoboranes ((R2N)2BH) could be prepared by mixing either imine-BH3 adducts or mono-aminoboranes with the corresponding free imines under the catalytic reaction conditions. Nevertheless, the most appropriate approach for the synthesis of unsymmetrical bis-aminoboranes was realized when imines were subjected to controlled hydroboration using mono-aminoboranes in the presence of the aluminum catalyst. Even though a majority of unsymmetrical bis-aminoboranes underwent the expected redistribution to their corresponding mono-aminoboranes, this process was averted in a few examples, which was attributed to the enhanced steric properties of the amino substituents.

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Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

Abstract: Bimetallic complexes [LW(CO)2(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H2 evolution from two neutral hydrides.

Cited by 15 publications

References 59 publications

Diverse Uses of the Reaction of Frustrated Lewis Pair (FLP) with Hydrogen

Diverse Uses of the Reaction of Frustrated Lewis Pair (FLP) with Hydrogen

Cooperative approaches in catalytic hydrogenation and dehydrogenation

Synthesis of Mono- and Acyclic Bis-aminoboranes via Controlled Hydroboration of Imines

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