N‐Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism

Li, Zhongshu; Chen, Xiaodan; Benkő, Zoltán; Liu, Liu; Ruiz, David A.; Peltier, Jesse L.; Bertrand, Guy; Su, Chen‐Yong; Grützmacher, Hansjörg

doi:10.1002/ange.201600903

Cited by 48 publications

(1 citation statement)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the character of the excitation for structure II is of av ery different form compared to that of the other structures,s ee Figure S51. Similar carbene-induced rearrangements of the [OCP] À anion to "fulminate-like" structural motifs have been described by Grützmacher [33,34] and Goicoechea [6] and coworkers for systems based on phosphorus, [33] silicon, [34] and boron. [6] With the synthesis of complexes 5a and 5b we could extend this type of isomerization chemistry to af-block metalbased system, yielding the first heavier group 15-group 16 analogue of asubstituted "fulminate-like" anion.…”

Section: Methodssupporting

confidence: 71%

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

et al. 2021

View full text Add to dashboard Cite

We present the η3‐coordination of the 2‐phosphaethynthiolate anion in the complex (PN)2La(SCP) (2) [PN=N‐(2‐(diisopropylphosphanyl)‐4‐methylphenyl)‐2,4,6‐trimethylanilide)]. Structural comparison with dinuclear thiocyanate‐bridged (PN)2La(μ‐1,3‐SCN)2La(PN)2 (3) and azide‐bridged (PN)2La(μ‐1,3‐N3)2La(PN)2 (4) complexes indicates that the [SCP]− coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*‐orbital of the [SCP]− ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP]− anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP]− ligand to form the first CAAC stabilized group 15–group 16 fulminate‐type complexes (PN)2La{SPC(RCAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP‐to‐SPC isomerization is proposed based on DFT calculations.

show abstract

Section: Methodssupporting

confidence: 71%

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

et al. 2021

View full text Add to dashboard Cite

show abstract

Metal‐Free Amine‐Mediated Oxidative Synthesis of Polysubstituted Imidazoles from Aryl Methyl Ketones, Ammonium Iodide or Benzylamine, and Hydrogen Peroxide

et al. 2017

View full text Add to dashboard Cite

A hydrogen peroxide (H2O2)‐promoted amine‐mediated oxidative coupling reaction between aryl methyl ketones and ammonium iodide leading to (4 or 5)‐aryl‐2‐benzoyl‐imidazole analogs has been developed; these analogs show highly potent antiproliferative activity and can be further developed as promising antitumor agents. This methodology features a one‐step process, metal‐free conditions, high atom economy, good functional group tolerance, and the use of economic and simple starting materials and oxidant. Moreover, the reaction can be scaled up without significant decrease of the yield. Furthermore, 1,2,4‐trisubstituted imidazoles, which are synthetically and pharmaceutically valuable compounds, are produced in the presence of benzylamine. A reasonable mechanism is proposed based on some control experiments.

show abstract

Eine monoanionische Arsenid‐Quelle: Decarbonylierung des 2‐Arsaethinolat‐Anions bei der Reaktion mit Stannylenen

Hinz

Goicoechea

2016

Angewandte Chemie

View full text Add to dashboard Cite

[6][7][8][9] Metathesereaktionen çffnen den Zugang zu verschiedenen Koordinationsverbindungen von Hauptgruppenelementen, [10] Actinoiden [11] und Übergangsmetallen [12][13][14] sowie zu Phosphaketen-Verbindungen der Gruppe-14-und Gruppe-15-Elemente (Silyl bis Plumbyl, [15,16] Germylenyl [17][18][19] und Phosphanyl, [20][21][22][23] C). Darüber hinaus wurde auch über Cycloadditionen mit Alkinen, [24] Ketenen und Carbodiimiden berichtet. [25,26] Unter diesen vielen Studien finden sich nur drei Beispiele,indenen PCO À als Quelle von Phosphid (P À )dient:gegenüber Cyclotrisilenen (unter Bildung von D,A bbildung 1), [27] Imidazoliumsalzen [28] und Isocyanaten.[29]Die Chemie des schwereren Homologen AsCO À (des 2-Arsaethinolat-Ions) ist weniger gut entwickelt, da es erst 2016 als [Na(18-Krone-6)]AsCO isoliert werden konnte.[30] Es konnte gezeigt werden, dass AsCO À mit Heteroallenen als Quelle von As À dienen kann und dass es [2+ +2]-Cycloadditionen eingeht.Die Reaktivitätd er schweren Homologen des Cyanats gegenüber koordinativ ungesättigten Metallzentren ist bislang jedoch noch nicht untersucht. Wire ntschlossen uns daher,d iese Reaktivitätv on PCO À und AsCO À am Beispiel des von der Gruppe um Power entwickelten Bis(terphenyl)stannylens Te r 2 Sn (Ter = 2,6-Bis(2,4,6-trimethylphenyl)phenyl) zu untersuchen, da dieses durch die sterisch anspruchsvollen Te rphenyl-Substituenten als Monomer vorliegt. [31,32] Überraschenderweise gibt es nur wenige Studien zur Chemie dieses Stannylens (Schema 1), das sowohl mit Wasser und Alkoholen [33] als auch mit Alkyl-Aluminium-, Alkyl-Gallium- [34] und Alkyl-Zink-Verbindungen [35] reagiert, aber nicht mit weißem Phosphor. [36] Hier berichten wir über die Reaktivitätv on PCO À und AsCO À gegenüber Ter 2 Sn und demonstrieren die thermische oder photolytische Decarbonylierung von AsCO À ,d as dadurch als Quelle von As À gegenüber einer molekularen Spezies dient. Abbildung 1. Beispielef ürdie Reaktivitätvon PCO À (R = z. B. H, Cyclohexyl, Prop-2-in-1-yl). Dipp = 2,6-Diisopropylphenyl;T ipp = 2,4,6-Triisopropylphenyl.

show abstract

N‐Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

Cited by 48 publications

References 46 publications

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

Metal‐Free Amine‐Mediated Oxidative Synthesis of Polysubstituted Imidazoles from Aryl Methyl Ketones, Ammonium Iodide or Benzylamine, and Hydrogen Peroxide

Eine monoanionische Arsenid‐Quelle: Decarbonylierung des 2‐Arsaethinolat‐Anions bei der Reaktion mit Stannylenen

Contact Info

Product

Resources

About

N‐Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

Cited by 48 publications

References 46 publications

η3‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

η3‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

Metal‐Free Amine‐Mediated Oxidative Synthesis of Polysubstituted Imidazoles from Aryl Methyl Ketones, Ammonium Iodide or Benzylamine, and Hydrogen Peroxide

Eine monoanionische Arsenid‐Quelle: Decarbonylierung des 2‐Arsaethinolat‐Anions bei der Reaktion mit Stannylenen

Contact Info

Product

Resources

About

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**

η³‐Coordination and Functionalization of the 2‐Phosphaethynthiolate Anion at Lanthanum(III)**