Addition of Hydrogen or Ammonia to a Low‐Valent Group 13 Metal Species at 25 °C and 1 Atmosphere

Zhu, Zhongliang; Wang, Xinping; Peng, Yang; Lei, Hao; Fettinger, James C.; Rivard, Eric; Power, Philip P.

doi:10.1002/anie.200805982

Cited by 129 publications

(110 citation statements)

References 37 publications

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“…NÀCb ondl engths to the aryl functionalities of the ligand backbonea re comparable in magnitude (1.429(2) and 1.440(2) )a nd slightly shorter than that to the methyl functionality 1.464(2) ,c onsistent with the reduced covalent radius of af ormally sp 2 -hybridised carbon atom compared to an sp 3 -hybridised species Dr = (0.03 ). [29] Scheme3.Formation of 9a/9 b from reaction of solutions of [7a/7 b][OTf] with potassium tert-butoxide.…”

Section: Reactivity Of 1a and 1b Towardselectrophilesmentioning

confidence: 82%

“…These novel phosphorus(V) compounds display similars tructures and 31 PNMR chemical shifts (À38.7 and À20.2 ppm for 4a and 5a,r espectively) to the EÀHa ctivation products that were obtained by reactiono f1a with H 2 Oa nd NH 3 .I nf act, compound 4a can be readily accessed by direct reactiono f1a with HOtBu.T he reactions proceeded rapidly (beforet he 31 PNMR spectra of the reaction mixtures were recorded) at room temperature affording the compounds in quantitative yields. Consequently,w ew ere unable to ascertain whether electrophilic association of the proton or benzylf unctionalities involved the ligand backbonep rior to migration of the functional group to the phosphorus centre.…”

mentioning

confidence: 82%

“…[1] Mostp rominent amongstt hese are alkyl(amino)c arbenes (AACs), [2] low oxidation state compounds of Groups13a nd 14, [3,4] and frustratedLewis pairs (FLPs). [5] Severalo ft he aforementioned compounds have also shown to be active in catalytic processes, such as the hydrogenation of imines,a lkenes and alkynes, [6] effectivelyh eralding an ew era in the chemistryo ft he p-block elements.…”

Section: Introductionmentioning

confidence: 99%

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On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Robinson

Rosa

et al. 2016

Chemistry A European J

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The ambiphilic nature of geometrically constrained Group 15 complexes bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand (ONO 3À )i se xplored. Despite their differing reactivity towards nucleophilic substrates with polarised element-hydrogen bonds (e.g.,N H 3 ), both the phosphorus(III), P(ONO)( 1a), anda rsenic(III), As(ONO)( 1b), compounds exhibit similar reactivity towards charged nucleophilesa nd electrophiles. Reactions of 1a and 1b with KOtBu or KNPh 2 afford anionicc omplexes in which the nucleophilic anion associates with the pnictogen centreÀ (Pn = P( 3a), As (3b)).C ompound 2a can subsequentlybe reacted with ap rotons ource or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(O-NO) (4a)a nd (tBuO)BzP(ONO) (5a), respectively,w hereas analogous arsenic(V) compounds are inaccessible.E lectrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1a and 1b,g iving rise to cationic species that can be rationalised as either ammonium salts or as amine-stabilised phospheniumo ra rsenium complexes( [Pn{ON(H)O}] + (Pn = P (6a), As (6b)) and [Pn{ON(Me)O}] + (Pn = P( 7a), As (7b)). Reactiono f1a with an acid bearing an ucleophilic counteranion (such as HCl) gives rise to ap hosphorus(V) compound HPCl(ONO) (8a), whereas the analogous reaction with 1b results in the addition of HCl across one of the AsÀOb onds to afford ClAs{(H)ONO} (8b). Functionalisation at both the pnictogenc entre and the ligand backbone is also possible by reactiono f7a/7b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn = P( 9a), As (9b)).T he ambiphilic reactivity of theseg eometrically constrainedc omplexes allowss omei nsight into the mechanism of reactivity of 1a towardssmall molecules, such as ammonia and water.

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Section: Reactivity Of 1a and 1b Towardselectrophilesmentioning

confidence: 82%

mentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

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On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Robinson

Rosa

et al. 2016

Chemistry A European J

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“…1 Several years later he also showed the addition of dihydrogen to distannynes to give tin(II) hydrides. [2][3][4][5][6][7][8] A notable surge in the reported reactivity of "frustrated Lewis pairs" (FLP) was kickstarted by Stephan et al, where they reported metalfree reversible hydrogen activation by the unquenched reactivity of a phosphine-borane ((C6H2Me3)2P(C6F4)B(C6F5)2), which features a Lewis acidic boron and Lewis basic phosphorus. 9 Since then, many different FLP systems have been developed 10 and reactivity with a variety of substrates has been observed, including B-H bonds, 11 CO2, 12,13 unsaturated bonds 10 and even catalytic, metal-free hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

et al. 2012

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The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo-and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding Nheterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P-N bond of the P-N-C-N framework.Computational analysis has provided corroborating evidence for the unwillingness of the halide abstraction reaction by demonstrating the exceptional electron acceptor properties of the target phosphenium cations and the underscoring strength of the P-X bond.

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“…1 Recently, interest in more environmentally benign, transition metal-free systems for activation of dihydrogen [2][3][4] has spiked, 5 primarily spurred by the development of the "Frustrated Lewis Pairs" (FLPs) concept. [6][7][8] In FLPs, Lewis acid/base combinations sterically prevented from forming strong classical adducts are capable of heterolytically activating H2.…”

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confidence: 99%

Dihydrogen Activation by Antiaromatic Pentaarylboroles

et al. 2010

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Facile metal-free splitting of molecular hydrogen (H 2 ) is crucial for the utilization of H 2 without the need for toxic transition-metal-based catalysts. Frustrated Lewis pairs (FLPs) are a new class of hydrogen activators wherein interactions with both a Lewis acid and a Lewis base heterolytically disrupt the hydrogen-hydrogen bond. Here we describe the activation of hydrogen exclusively by a boron-based Lewis acid, perfluoropentaphenylborole. This antiaromatic compound reacts extremely rapidly with H 2 in both solution and the solid state to yield boracyclopent-3-ene products resulting from addition of hydrogen atoms to the carbons R to boron in the starting borole. The disruption of antiaromaticity upon reaction of the borole with H 2 provides a significant thermodynamic driving force for this new metal-free hydrogen-splitting reaction.

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Addition of Hydrogen or Ammonia to a Low‐Valent Group 13 Metal Species at 25 °C and 1 Atmosphere

Cited by 129 publications

References 37 publications

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

Dihydrogen Activation by Antiaromatic Pentaarylboroles

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