Base-induced reversible H<sub>2</sub> addition to a single Sn(<scp>ii</scp>) centre

Turnell-Ritson, Roland C.; Sapsford, Joshua S.; Cooper, Robert T.; Lee, Stella S.; Földes, Tamás; Hunt, Patricia A.; Pápai, Imre; Ashley, Andrew E.

doi:10.1039/c8sc03110j

Cited by 19 publications

(17 citation statements)

References 56 publications

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“…The reaction starts with the abstraction of the most acidic urea proton by the base, which is a slightly endergonic process. We obtained good correlation between the p K a of the bases and the energonicity of the deprotonation step . The levels obtained with the strongest base (BEMP) are shown in blue.…”

Section: Resultsmentioning

confidence: 65%

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

et al. 2019

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The first organo-catalyzed synthesis of imidazolidin-2-ones and imidazol-2-ones via intramolecular hydroamidation of propargylic ureas is reported. The phosphazene base BEMP turned out to be the most active organo-catalyst compared with guanidine and amidine bases. Excellent chemo- and regioselectivities to five-membered cyclic ureas have been achieved under ambient conditions, with a wide substrate scope and exceptionally short reaction times (down to 1 min). A base-mediated isomerization step to an allenamide intermediate is the most feasible reaction pathway to give imidazol-2-ones, as suggested by DFT studies.

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Section: Resultsmentioning

confidence: 65%

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

et al. 2019

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“…Pápai, Ashley and co‐workers investigated the base induced reversible hydrogenation of diorganostannylene [Sn{CH(SiMe 3 ) 2 } 2 ]. Hydrogenation was observed at 4 bar H 2 in the presence of Et 3 N acting as a catalyst and the elimination of H 2 was demonstrated at room temperature in reaction of the dihydride with DBU [31] . Bis(boryl) substituted stannylene was shown to add hydrogen at rt by Aldridge and co‐workers [32] …”

Section: Resultsmentioning

confidence: 99%

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

et al. 2021

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Tetrylidynes [(Me3P)2(Ph3P)Rh≡SnAr*] (10) and [(Me3P)2(Ph3P)Rh≡PbAr*] (11) are accessed for the first time via dehydrogenation of dihydrides [(Ph3P)2RhH2SnAr*] (3) and [(Ph3P)2RhH2PbAr*] (7) (Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐triisopropylphenyl), respectively. Tin dihydride 3 was either synthesized in reaction of the dihydridostannate [Ar*SnH2]− with [(Ph3P)3RhCl] or via reaction between hydrides [(Ph3P)3RhH] and 1/2 [(Ar*SnH)2]. Homologous lead hydride [(Ph3P)2RhH2PbAr*] (7) was synthesized analogously from [(Ph3P)3RhH] and 1/2 [(Ar*PbH)2]. Abstraction of hydrogen from 3 and 7 supported by styrene and trimethylphosphine addition yields tetrylidynes 10 and 11. Stannylidyne 10 was also characterized by 119Sn Mössbauer spectroscopy. Hydrogenation of the triple bonds at room temperature with excess H2 gives the cis‐dihydride [(Me3P)2(Ph3P)RhH2PbAr*] (12) and the tetrahydride [(Me3P)2(Ph3P)RhH2SnH2Ar*] (14). Complex 14 eliminates spontaneously one equivalent of hydrogen at room temperature to give the dihydride [(Me3P)2(Ph3P)RhH2SnAr*] (13). Hydrogen addition and elimination at stannylene tin between complexes 13 and 14 is a reversible reaction at room temperature.

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“…Pápai, Ashley und Mitarbeiter beschäftigten sich mit der baseninduzierten, reversiblen Hydrierung des Diorganostannylens [Sn{CH(SiMe 3 ) 2 } 2 ]. Eine Hydrierung war bei 4 bar H 2 in Anwesenheit von Et 3 N als Katalysator zu sehen, während die Eliminierung von H 2 bei Raumtemperatur in einer Reaktion des Dihydrids mit DBU demonstriert wurde [31] …”

Section: Ergebnisse Und Diskussionunclassified

“…Eine Hydrierung war bei 4bar H 2 in Anwesenheit von Et 3 Na ls Katalysator zu sehen, während die Eliminierung von H 2 bei Raumtemperatur in einer Reaktion des Dihydrids mit DBUd emonstriert wurde. [31] Füre in bis(boryl)substituiertes Stannylen konnten Aldridge und Mitarbeiter die Addition von Wasserstoff bei Raumtemperatur zeigen. [32] Die Hydrierungsprodukte 12, 13 und 14 wurden mittels Einkristall-Rçntgenstrukturanalyseu nd NMR-Spektroskopie analysiert.…”

Section: Angewandte Chemieunclassified

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Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

et al. 2021

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Die Tetrylidine [(Me3P)2(Ph3P)Rh≡SnAr*] (10) und [(Me3P)2(Ph3P)Rh≡PbAr*] (11) wurden erstmalig über eine Dehydrierung der Dihydride [(Ph3P)2RhH2SnAr*] (3) und [(Ph3P)2RhH2PbAr*] (7) (Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐Triisopropylphenyl) erhalten. Das Zinn‐Dihydrid 3 wurde entweder durch eine Reaktion des Dihydrostannats [Ar*SnH2]− mit [(Ph3P)3RhCl] oder durch Reaktion zwischen den Hydriden [(Ph3P)3RhH] und 1/2 [(Ar*SnH)2] synthetisiert. Das homologe Bleihydrid [(Ph3P)2RhH2PbAr*] (7) war analog aus [(Ph3P)3RhH] und 1/2 [(Ar*PbH)2] zugänglich. Die Eliminierung von Wasserstoff aus 3 und 7 mittels Styrol und anschließende Addition von Trimethylphosphan liefert die Tetrylidine 10 und 11. Das Stannylidin 10 wurde auch durch 119Sn‐Mössbauer‐Spektroskopie charakterisiert. Die Hydrierung dieser Dreifachbindungen mit überstöchiometrischen Mengen Wasserstoff bei Raumtemperatur liefert das cis‐Dihydrid [(Me3P)2(Ph3P)RhH2PbAr*] (12) und das Tetrahydrid [(Me3P)2(Ph3P)RhH2SnH2Ar*] (14). Komplex 14 eliminiert bei Raumtemperatur spontan ein Äquivalent Wasserstoff unter Bildung des Dihydrids [(Me3P)2(Ph3P)RhH2SnAr*] (13). Die Wasserstoffaddition und ‐eliminierung am Stannylen‐Zinnatom zwischen Komplex 13 und 14 ist bei Raumtemperatur reversibel.

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Base-induced reversible H₂ addition to a single Sn(ii) centre

Abstract: A ‘frustrated Lewis pair’-type mechanism allows the first observation of reversible H2 addition to a single-site main-group complex.

Cited by 19 publications

References 56 publications

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

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Base-induced reversible H2 addition to a single Sn(ii) centre

Abstract: A ‘frustrated Lewis pair’-type mechanism allows the first observation of reversible H2 addition to a single-site main-group complex.

Cited by 19 publications

References 56 publications

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

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Base-induced reversible H₂ addition to a single Sn(ii) centre

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)

Synthese und Hydrierung schwerer Homologe eines Rhodium‐Carbins: [(Me₃P)₂(Ph₃P)Rh≡E‐Ar*] (E=Sn, Pb)