Hydrosilylation of Alkynes by Ni(CO)<sub>3</sub>‐Stabilized Silicon(II) Hydride

Stoelzel, Miriam; Präsang, Carsten; Inoue, Shigeyoshi; Enthaler, Stephan; Drieß, Matthias

doi:10.1002/anie.201105722

Cited by 69 publications

(43 citation statements)

References 61 publications

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“…A further highlight in the reactivity of 44 is its ability, after suitable synthetic modification, to stoichiometrically effect the hydrosilylation of alkynes (Scheme 10) [44,45]. In this instance, reaction of 44 with HCl initially affords 52, which by treatment with Li[HBEt 3 ] can be readily converted to 53.…”

Section: Free N-heterocyclic Silylenes (Nhsis) and Their Reactivity Tmentioning

confidence: 99%

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Blom

Drieß

2013

Structure and Bonding

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*2 Si: (Cp* ¼ η 5 -C 5 Me 5 ), the first isolable Si(II) compound, and later in 1994 with the discovery of the first N-heterocyclic silylene by West and Denk, heralding the beginning of a bourgeoning era in low-valent silicon chemistry. Since these and other key discoveries, massive advances have been made in understanding and elucidating the nature of these reactive compounds, and their ability, for example, to activate small molecules, or behave as ligands in transition metal complexes which can perform a variety of catalytic or stoichiometric transformations. In this chapter, recent advances in silylene chemistry will be presented, with a particular focus on developments in the last 10 years approximately. A key emphasis will rest on the reactivity of isolable silylenes, including their coordination towards metals, with respect to small molecule bond activation, and potential catalytic transformations. Although metalcoordinated silylene complexes have been shown to be catalytically useful in a variety of transformations, metal-free catalysis with silylenes is still a target.

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Section: Free N-heterocyclic Silylenes (Nhsis) and Their Reactivity Tmentioning

confidence: 99%

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Blom

Drieß

2013

Structure and Bonding

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“…[20] Power et al could show that amore complex tin cluster is able to stoichiometrically react with dihydrogen (E). [22,23] Aldridge and co-workers elegantly demonstrated the activation of H 2 and NH 3 and the reduction of carbon dioxide employing an electron-poor gallium center (F). [22,23] Aldridge and co-workers elegantly demonstrated the activation of H 2 and NH 3 and the reduction of carbon dioxide employing an electron-poor gallium center (F).…”

mentioning

confidence: 99%

Metal‐Free Activation of Hydrogen, Carbon Dioxide, and Ammonia by the Open‐Shell Singlet Biradicaloid [P(μ‐NTer)]₂

2016

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The Group 15 open-shell singlet biradicaloid [P(μ-NTer)]2 (Ter=2,6-bis(2,4,6-trimethylphenyl)phenyl) was utilized in the activation of stable small molecules. Fast reactions with H2 , CO2 , and NH3 were observed. Dihydrogen easily added to [P(μ-NTer)]2 , yielding [HP(μ-NTer)]2 under ambient conditions whereas reversible release of molecular hydrogen was observed at slightly elevated temperatures (T>60 °C). As [P(μ-NTer)]2 is a species with phosphorus in the unusual formal oxidation state +II, it is capable of reducing carbon dioxide to afford a zwitterionic compound, [OP(μ-NTer)2 P], and carbon monoxide. The reaction of [P(μ-NTer)]2 with ammonia led to the formation of an azadiphosphiridine after rearrangements of the central P2 N2 heterocycle.

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“…Ein anderes interessantes Beispiel ist die Aktivierung von PH 3 und AsH 3 durch ein Silylen ( C ), das Driess et al. untersuchten . Aldridge et al.…”

Section: Methodsunclassified

Metallfreie Aktivierung von Wasserstoff, Kohlenstoffdioxid und Ammoniak durch das offenschalige Singulett‐Biradikaloid [P(μ‐NTer)]₂

Hinz¹,

Schulz

Villinger

2016

Angewandte Chemie

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Das offenschalige Singulett-Biradikaloid [P(m-NTer)] 2 (Ter = 2,6-Bis(2,4,6-trimethylphenyl)phenyl) wurde in der Aktivierung kleiner stabiler Moleküle eingesetzt, wobei schnelle Reaktionen mit H 2 ,CO 2 und NH 3 beobachtet wurden. Wasserstoff reagiert bei Raumtemperatur mit [P(m-NTer)] 2 zu [HP(m-NTer)] 2 ,w ohingegen die Freisetzung von Wasserstoff bei Temperaturen oberhalb 60 8 8Cg efunden wurde. [P(m-NTer)] 2 ,eine Verbindung mit Phosphor in der ungewçhnlichen Oxidationsstufe + II, konnte Kohlenstoffdioxid reduzieren, wobei die zwitterionische Verbindung [OP(m-NTer) 2 P] und Kohlenstoffmonoxid erhalten wurden. Die Reaktion von [P(m-NTer)] 2 mit Ammoniak führte zur Bildung eines Azadiphosphiridins,nachdem der zentrale P 2 N 2 -Heterocyclus eine Umlagerung durchlaufen hatte. Die Aktivierung kleiner Moleküle wie Wasserstoff, [1] Kohlenstoffdioxid [2] und Ammoniak [3] ist fürv iele chemische Reaktionen von großer Bedeutung, insbesondere katalytische Reaktionen mit leicht verfügbaren Ausgangsmaterialien. Häufig kçnnen Übergangsmetallkomplexe den notwendigen Aktivierungsschritt dieser relativ stabilen kleinen Moleküle vollziehen. Durch Fortschritte in der Hauptgruppenchemie in den letzten zehn Jahren konnte eine ähnliche Reaktivität auch ohne Übergangsmetallkomplexee rzielt werden, indem frustrierte Lewis-Paare (FLPs), [2]

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Hydrosilylation of Alkynes by Ni(CO)₃‐Stabilized Silicon(II) Hydride

Cited by 69 publications

References 61 publications

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Metal‐Free Activation of Hydrogen, Carbon Dioxide, and Ammonia by the Open‐Shell Singlet Biradicaloid [P(μ‐NTer)]₂

Metallfreie Aktivierung von Wasserstoff, Kohlenstoffdioxid und Ammoniak durch das offenschalige Singulett‐Biradikaloid [P(μ‐NTer)]₂

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Hydrosilylation of Alkynes by Ni(CO)3‐Stabilized Silicon(II) Hydride

Cited by 69 publications

References 61 publications

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Metal‐Free Activation of Hydrogen, Carbon Dioxide, and Ammonia by the Open‐Shell Singlet Biradicaloid [P(μ‐NTer)]2

Metallfreie Aktivierung von Wasserstoff, Kohlenstoffdioxid und Ammoniak durch das offenschalige Singulett‐Biradikaloid [P(μ‐NTer)]2

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Hydrosilylation of Alkynes by Ni(CO)₃‐Stabilized Silicon(II) Hydride

Metal‐Free Activation of Hydrogen, Carbon Dioxide, and Ammonia by the Open‐Shell Singlet Biradicaloid [P(μ‐NTer)]₂

Metallfreie Aktivierung von Wasserstoff, Kohlenstoffdioxid und Ammoniak durch das offenschalige Singulett‐Biradikaloid [P(μ‐NTer)]₂