A Gallium‐Substituted Distibene and an Antimony‐Analogue Bicyclo[1.1.0]butane: Synthesis and Solid‐State Structures

Abstract

RGa {R=HC[C(Me)N(2,6-iPr2C6H3)]2} reacts with Sb(NMe2)3 with insertion into the Sb-N bond and elimination of RGa(NMe2)2 (2), yielding the Ga-substituted distibene R(Me2N)GaSb=SbGa(NMe2 )R (1). Thermolysis of 1 proceeded with elimination of RGa and 2 and subsequent formation of the bicyclo[1.1.0]butane analogue [R(Me2N)Ga]2Sb4 (3).

From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

“…1 and 4 show syn,syn configurations with the halogen atoms orienting toward the middle of the Ga-E-Ga skeleton. The Ga–Sb bond lengths in 1 [2.5899(4), 2.5909(3) Å] are comparable to those in [L(X)Ga] 2 Sb 4 [X = Cl 2.6008(13) Å, NMe 2 2.5975(5) Å] 33,36 , but shorter than in 2 [2.6265(11) Å], 3 [2.6979(2) Å], Ga-substituted distibenes [L(X)Ga] 2 Sb 2 [X = NMe 2 2.6477(3) Å, NMeEt 2.6433(6) Å, Cl 2.6461(2) Å] 33,36 , the sum of the covalent radii (Ga 1.24 Å; Sb 1.40 Å) 38 , as well as Lewis acid-base adducts R 3 Ga-SbR' 3 (2.84–3.02 Å) and heterocycles [R 2 GaSb(SiMe 3 ) 2 ] x ( x  = 2, 3; 2.65–2.76 Å) 39 . The Ga–Bi bond lengths in 4 [2.6640(9), 2.6663(9) Å] agree well with those of [L(OSO 2 CF 3 )Ga] 2 Bi 2 (2.655(1) Å] 40 , but are shorter than those in [L(OC 6 F 5 )Ga] 2 Bi 2 [2.693(6) Å] 40 , L(Et)GaBiEt 2 [2.6959(3) Å] 41 , LGa(BiEt 2 ) 2 [2.6961(6) Å, 2.7303(10) Å] 32 and the sum of the covalent radii (Ga 1.24 Å; Bi 1.51 Å) 38 .…”

“…Thermolysis at 120 °C for 30 h yielded LGa and distibene [L(Cl)Ga] 2 Sb 2 , which further underwent LGaCl 2 and LGa elimination and finally formed [L(Cl)Ga] 2 Sb 4 (Supplementary Figs. 24–26) 33 . 1 H and 13 C NMR spectra of 5 show the expected resonances of the organic substituents (Supplementary Figs.…”

Lewis acid–base adducts of group 13 elements: synthesis, structure and reactivity toward benzaldehyde

“…LGa with different main group metal compounds including InEt 3 , [15] BiEt 3 , [16] Sb(NMe 2 ) 3 , [17] E 2 Et 4 (E = Sb, Bi) [18] as well as TeEt 2 and Te 2 Et 2 , [19] respectively, in detail. We herein expanded our investigations on reactions of LGa with different group 13 Lewis acids M(C 6 F 5 ) 3 (M = B, Al, Ga) and also report on their potential use for small molecule activation reactions such as benzaldehyde.…”

Intermetalloid Clusters: Molecules and Solids in a Dialogue

“…[91] Reduction of SnCl 2 by low-valent Ga I (ddp) (ddp = 2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)i-mino}-2-pentene) enables the formation of [Sn 17 {GaCl-(ddp)} 4 ], al igand-stabilized, but empty counterpart of the endohedrally filled dimer [Co 2 @Sn 17 ] 5À discussed above. Afeature which was also found to be of use in the preparation of the heterometallic gallium and [93] and is commonly employed in the preparation of the later-on discussed Hume-Rothery type cluster compounds combining group 12 and 13 elements with d-block metals (section 4). Afeature which was also found to be of use in the preparation of the heterometallic gallium and [93] and is commonly employed in the preparation of the later-on discussed Hume-Rothery type cluster compounds combining group 12 and 13 elements with d-block metals (section 4).…”