Synthesis of the sterically encumbering terphenyl silyl and alkyl amines (R=Me and SiMe3), their lithium derivatives , and the tertiary amine

Wright, Robert J.; Steiner, Jochen; Beaini, Samar; Power, Philip P.

doi:10.1016/j.ica.2005.10.015

Cited by 44 publications

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“…It is known, that the formation of a specific aminopnictane, iminopnictane or its dimer, the cyclodipnictadiazane, can be influenced by the presence of specific substituents (depending on the steric strain) on the amine and by the use of lithium amides rather than amines. [1] In this context, it was of interest to study the effect of a bulky group, such as the terphenyl group (Ter = 2,6-Mes 2 C 6 H 3 , Mes = 2,4,6-Me 3 C 6 H 2 ) [12] on the reaction products.To obtain 1,3-dichloro-2,4-di(m-terphenyl)cyclo-1,3dibisma-2,4-diazane, [TerNÀBiCl] 2 , in a two-step reaction, first the dichloro(m-terphenylamino)bismutane (1) had to be prepared in the reaction of terphenylaniline, TerNH 2 , with n-BuLi in the presence of BiCl 3 [Eq.(2)] at ambient temperatures. This reaction gave 1 as a red, crystalline solid in over 80 % yield (m.p.…”

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Dichlorocyclodibismadiazane

2010

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Four-membered pnictogen-nitrogen heterocycles of the type [ClE(m-NR)] 2 (E = element of Group 15) are known as 1,3-dichlorocyclo-1,3-dipnicta(III)-2,4-diazanes.[1] Especially the phosphorus species play a major role in preparative phosphorus-nitrogen chemistry, for example, in the preparation of macrocycles, polymers, main-group complexes, and ringtransformation reactions or the generation of cyclic binary PN cations. [2][3][4] As early as 1894 Michaelis and Schroeter discovered the first cyclo-1,3-diphospha(III)-2,4-diazane when they treated aniline hydrochloride with an excess of PCl 3 for two days under reflux [Eq. (1)].[5] However, they thought they had isolated the monomeric species, C 6 H 5 À N = P À Cl. Today we know that the dimer represents the stable form of phenyl substituted 1,3-dichlorocyclo-1,3-diphospha(III)-2,4-diazane. [2a, 3, 6, 7] The chemistry of the heavier pnictogen analogues (As, Sb, Bi) of this classic inorganic E 2 N 2 ring system has only slowly been developed in the last 50 years. [8][9][10] The simplest cyclodipnicta(III)diazanes are the dichloro derivatives, [ClE-(m-NR)] 2 , (A, Scheme 1) and are only known for E = P, As, and Sb, while bis(organoamino) derivatives B and bis(dimethylamino) derivatives C are observed for the whole series E = P-Bi.[1] The slow progress, especially in the chemistry of Bi 2 N 2 ring systems compared to that of P 2 N 2 rings can be attributed to the lability of BiÀN bonds. Hence, Chivers et al. pointed out, that "The discovery of a suitable synthesis of dichloro derivatives of type A for bismuth would be a significant step forward".[1] Herein, we report the synthesis and full characterization of the first dichlorocyclodibismadiazane.A typical route to cyclodipnictadiazanes is the facile HCl elimination, between primary amines and trichloropnictanes to give aminopnictanes. However, the isolation of the amination products is complicated because of the coincident formation of monoaminodichloro-, diaminochloro-, and trisaminopnictanes, [11] as well as the possibility for formation of the iminopnictanes. It is known, that the formation of a specific aminopnictane, iminopnictane or its dimer, the cyclodipnictadiazane, can be influenced by the presence of specific substituents (depending on the steric strain) on the amine and by the use of lithium amides rather than amines. [1] In this context, it was of interest to study the effect of a bulky group, such as the terphenyl group (Ter = 2,6-Mes 2 C 6 H 3 , Mes = 2,4,6-Me 3 C 6 H 2 ) [12] on the reaction products. To obtain 1,3-dichloro-2,4-di(m-terphenyl)cyclo-1,3-dibisma-2,4-diazane, [TerNÀBiCl] 2 , in a two-step reaction, first the dichloro(m-terphenylamino)bismutane (1) had to be prepared in the reaction of terphenylaniline, TerNH 2 , with n-BuLi in the presence of BiCl 3 [Eq. (2)] at ambient temperatures. This reaction gave 1 as a red, crystalline solid in over 80 % yield (m.p. 189 8C (decomp)). The second step included a complex reaction of 1 in THF with DBU (1,8-diazabicyclo-[5.4.0]undec-7-ene) at low temp...

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Dichlorocyclodibismadiazane

2010

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“…28 To increase the steric bulk of these compounds one of the nitrogen-substituted protons can be substituted with a trimethylsilyl or methyl group providing 2,6-Mes 2 C 6 H 3 N(SiMe 3 )H or 2,6-Mes 2 C 6 H 3 N(Me)H, respectively. Their utilisation is still extremely limited compared to the m-terphenyls, but they are showing that they are versatile ligands for the main group elements, and can provide a degree of tuning with regards to the steric pocket they provide.…”

Section: M-terphenyl Anilide and Imide Ligandsmentioning

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“…43 The reaction between M{N(SiMe 3 ) 2 } 2 and two equivalents of 2,6-Mes 2 C 6 H 3 NH 2 in toluene yielded the rare monomeric (28), which is rare for the two-coordinate derivatives of these Group 14 metals. 43 The reaction between M{N(SiMe 3 ) 2 } 2 and two equivalents of 2,6-Mes 2 C 6 H 3 NH 2 in toluene yielded the rare monomeric (28), which is rare for the two-coordinate derivatives of these Group 14 metals.…”

Section: Group 14 Complexesmentioning

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Extremely bulky amide ligands in main group chemistry

Kays

2016

Chem. Soc. Rev.

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The search for extremely sterically demanding monodentate amide ligands to access main group complexes in low-coordination numbers and highly reactive bonding modes is an area of intense research interest. The recent development of three classes of sterically demanding, monodentate amide ligands - the m-terphenyl anilides [N(R){C6H3Ar2-2,6}](-) (Ar = aryl, R = H, methyl, silyl), substituted carbazol-9-yl and the extremely bulky amides [N(R)(Ar')](-) (Ar' = 2,6-{C(H)Ph2}-4-R'-C6H2, R = silyl, aryl, silyloxy, R' = alkyl) is facilitating the isolation of stable species with new coordination modes for the main group elements. These compounds are of fundamental importance not only from the investigation of their structure and bonding, but also the investigation of their reactivity highlights the potential for small molecule activation chemistry under mild conditions and applications in catalysis. This review reports on the recent developments for these compounds with emphasis on their synthesis, structure and reactivity.

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“…[1] Daher interessierte uns der Einfluss von sperrigen Resten wie dem Terphenylrest (Ter; = 2,6-Mes 2 C 6 H 3 , Mes = 2,4,6-Me 3 C 6 H 2 ) [12] auf die Reaktionsprodukte.…”

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Ein Dichlorcyclodibismadiazan

2010

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Unter den viergliedrigen Pniktogen-Stickstoff-Heterocyclen des Typs [ClE(m-NR)] 2 (E = Element der Gruppe 15), die als 1,3-Dichlorcyclo-1,3-dipnikta(III)-2,4-diazane benannt werden, [1] spielen besonders die Phosphorderivate eine bedeutende Rolle, z. B. für die Synthese von Makrocyclen, Polymeren, Hauptgruppenkomplexen, in Ringtransformationsreaktionen oder zur Synthese von cyclischen binären PN-Kationen. [2][3][4] Bereits im Jahr 1894 entdeckten Michaelis und Schroeter das erste Cyclo-1,3-diphospha(III)-2,4-diazan, als sie Anilinhydrochlorid mit PCl 3 im Überschuss zwei Tage unter Rück-fluss kochten [Gl. (1)].[5] Die Autoren dachten jedoch, dass sie die monomere Verbindung, C 6 H 5 À N = P À Cl, synthetisiert hätten. Heute wissen wir, dass das Dimer die stabile Form des phenylsubstituierten 1,3-Dichlorcyclo-1,3-diphospha(III)-2,4-diazans ist. [2a, 3, 6, 7] Die Chemie der schweren Pniktogenanaloga (As, Sb, Bi) dieses klassischen anorganischen E 2 N 2 -Ringsystems hat sich in den letzten 50 Jahren nur sehr langsam entwickelt.[8-10] Die einfachsten Cyclodipnikta(III)-diazane sind die Dichlorderivate [ClE(m-NR)] 2 (A, Schema 1), die nur für E = P, As und Sb bekannt sind, während die Bis(organoamino)derivate B und Bis(dimethylamino)derivate C für die ganze Reihe E = P-Bi beobachtet wurden.[1] Der langsame Fortschritt besonders in der Chemie des Bi 2 N 2 -Ringsystems im Vergleich zur Vielfalt in der Chemie der analogen P 2 N 2 -Ringe kann der Schwäche der Bi-N-Bindung zugeschrieben werden. Aus diesem Grund schlussfolgerten Chivers et al., dass "the discovery of a suitable synthesis of dichloro derivatives of type A for bismuth would be a significant step forward".[1] Im Folgenden berichten wir über die Synthese und vollständige Charakterisierung des ersten Dichlorcyclodibismadiazans.Ein einfacher Weg zu Cyclodipniktadiazanen ist die HClEliminierung, durch die primäre Amine und Trichlorpniktane zu Aminopniktanen verknüpft werden können. Allerdings ist die Isolierung der Aminierungsprodukte wegen der gleichzeitigen Bildung von Monoaminodichlor-, Diaminochlor-und Trisaminopniktanen kompliziert.[11] Ebenso kann es zur Bildung von Iminopniktanen kommen. Es ist bekannt, dass die Bildung eines spezifischen Aminopniktans, Iminopniktans oder deren Dimere, der Cyclodipniktadiazane, durch die Anwesenheit spezifischer Substituenten (in Abhängigkeit vom sterischen Anspruch) am Amin und durch die Verwendung von Lithiumamiden anstelle von Aminen beeinflusst werden kann.[1] Daher interessierte uns der Einfluss von sperrigen Resten wie dem Terphenylrest (Ter; = 2,6-Mes 2 C 6 H 3 , Mes = 2,4,6-Me 3 C 6 H 2 ) [12] auf die Reaktionsprodukte.Die Schema 1. Bekannte Cyclodipnikta(III)-diazane: A: E= P, As, Sb; B und C: E= P, As, Sb, Bi; R, R' = Aryl, Alkyl.

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Synthesis of the sterically encumbering terphenyl silyl and alkyl amines (R=Me and SiMe3), their lithium derivatives , and the tertiary amine

Cited by 44 publications

References 52 publications

Dichlorocyclodibismadiazane

Dichlorocyclodibismadiazane

Extremely bulky amide ligands in main group chemistry

Ein Dichlorcyclodibismadiazan

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