A General Synthetic Pathway to Lewis Base-Stabilized, MonomericGroup 13/15 Compounds

Abstract

Reactions of an equimolar amount of 4-(dimethylamino)pyridine (dmap) with several Al−E heterocycles [R 2 AlE(SiMe 3 ) 2 ] x (E = P, As; R = Me, x = 3; R = Et, x = 2) and Ga−Sb heterocycles [R 2 GaSb(SiMe 3 ) 2 ] x (R = Me, x = 3; R = Et, x = 2) in hexane offers a general pathway for the formation of mono-

A General Pathway for the Synthesis of Gallastibenes containing Ga=Sb Double Bonds

“…1 – 4 show the shortest Ga−Sb bonds for compounds containing threefold‐coordinated Sb atoms. For instance, the Ga2−Sb1 bonds are significantly shorter than the Ga−Sb σ ‐bonds found in Lewis acid base adducts, [R 2 GaSbR′ 2 ] 3 heterocycles (2.663(2)–2.722(3) Å) and monomeric [(dmap)Et 2 GaSb(SiMe 3 ) 2 ] (2.648(1) Å; dmap=4‐dimethylaminopyridine) with threefold‐coordinated Sb atom . They are also shorter in comparison to Ga−Sb bonds observed in (LGa) 2 Sb 4 (2.6637(11)–2.6779(11) Å), [L(X)GaSb] 2 (X=NMe 2 2.6200(4) Å; NMeEt 2.6169(5) Å; Cl 2.58178(19) Å), [{L(X)Ga} 2 ( μ , η 1:1 ‐Sb 4 )] (X=NMe 2 2.5975(5) Å; Cl 2.6008(13) Å), and base‐stabilized [Cl( n ‐Pr 2 PhP)GaSbSi‐ i Pr 3 ] 2 (2.635(1)–2.655(1) Å) .…”

Synthesis, Structure, and Reactivity of Ga‐Substituted Distibenes and Sb‐Analogues of Bicyclo[1.1.0]butane

“…This finding most likely results from the electron‐withdrawing effect of the Cl‐substituent, which enhances the Lewis acidity of the Ga atom. The Ga−Sb bonds are significantly shorter than Ga−Sb single bonds as observed in Lewis acid‐base adducts of the general type R 3 Sb‐GaR′ 3 , the base‐stabilized monomer dmap‐Ga(Et) 2 Sb(SiMe 3 ) 2 (dmap=4‐NMe 2 ‐pyridine; 2.648(1) Å) and in heterocyclic compounds such as [R 2 GaSbR′ 2 ] x , in which the Ga−Sb bond lengths were found to range from 2.666–2.772 Å . They are also slightly shorter than the sum of the covalent radii (Ga=1.24; Sb=1.40 Å) .…”

Synthese und Festkörperstruktur eines Ga‐substituierten Distibens und eines Sb‐Analogons von Bicyclo[1.1.0]butan

“…Der Sb‐Sb‐Ga‐Bindungswinkel (94.71(1)°) stimmt gut mit dem berechneten Sb‐Sb‐H‐Winkel in HSbSbH (93.0°)20 sowie den experimentell ermittelten Werten in Distibenen ArSbSbAr überein 19. Das Ga‐Atom des C 3 N 2 Ga‐Rings liegt leicht außerhalb der Ringebene (Abweichung aus der Ebene 0.6468(17) Å) und die Ga‐Sb‐Bindungslänge (2.6200(4) Å) ist vergleichbar mit der Summe der Kovalenzradien (Ga=1.24 Å; Sb=1.40 Å)21 sowie experimentell ermittelten Bindungslängen in Verbindungen mit Ga‐Sb‐σ‐Bindung wie [Me 2 GaSbR′ 2 ] 3 (R′=SiMe 3 , 2.6773(5)–2.7144(5) Å;22a Me, 2.666(1)–2.682(1) Å;22b i Pr, 2.669(1)–2.694(1) Å22b) und [(dmap)Et 2 GaSb(SiMe 3 ) 2 ] (2.648(1) Å; dmap=4‐Dimethylaminopyridin) 23. Die Struktur von 2 (Abbildung S12) ist identisch mit der von RGa(NH 2 ) 2 24.…”