Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me₂NCH₂)C₆H₄]₂Sb Fragment

Abstract

Compounds containing the [2‐(Me2NCH2)C6H4]2Sb moiety were prepared by using R2SbX [X = Cl (1), Br (2)] as starting materials. The reaction of 1 with Me3SiCH2MgCl gave the mixed alkyl–aryl stibine R2SbCH2SiMe3 (3). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S8 resulted in the isolation of (R2Sb)2E [E = O (4), S (5)]. Compound 5 is also formed from R2SbCl and Na2S. The reaction of 4 with [W(CO)5(thf)] gives the unexpected complex [(R2SbOH)W(CO)5] (6). The new compounds were investigated by IR, 1H, and 13C NMR spectroscopy, as well as by mass spectrometry. The structures of 3–6 were determined by single‐crystal X‐ray diffraction. For compounds 3–5, both nitrogen atoms from the pendant arms are involved in intramolecular N→Sb coordination, which results in distorted square‐pyramidal (C,N)2SbC or (C,N)2SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N···H–O bonding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

“…[14] Unfortunately, only limited information on their solid state structures are available. To the best of our knowledge, a very few sulfane derivatives (R 2 Sb) 2 S (R = Me, [88] 2-Me 2 NCH 2 C 6 H 4 [89] ) and (R 2 Bi) 2 S (R = (Me 3 Si) 2 CH, [63] 2,4,6-Me 3 C 6 H 2 , [11] 2-(Me 2 NCH 2 )C 6 H 4 , [13] RN(CH 2 C 6 H 4 ) 2 , R = Ph, Cy, t-Bu [90] ) have been structurally characterized, whereas analogous compounds containing the heavier group 16 elements, Se and Te, remained unknown for a long time. Only recently, progress was made on the structural characterization of such compounds.…”

“…Aside from the previously mentioned bis(dialkylstibanyl)sulfanes (R 2 Sb) 2 S, [88,89] four metal compounds containing (R 2 Sb) 2 S and (R 2 Sb) 2 Se ligands were structurally characterized:…”

Synthesis, Structure and Applications of Hypervalent Organoantimony Compounds Having Intramolecular E→Sb (E = N, O, S) Coordinations

“…[2-(Me 2 NCH 2 )C 6 H 4 ] n R 3-n Sb [n = 1, R = Ph (5), Mes (6); n = 2, R = Ph (7), Mes (8), CH 2 SiMe 3 (9)] and [2-(Me 2 NCH 2 )C 6 H 4 ]PhMesSb (10) [50,51]. Compounds 5-10 exhibit chirality and crystallize as racemic mixtures.…”

“…A thermal ellipsoid plot (30% probability level) of compound 52, and hydrogen atoms are omitted for clarity.Reduction of monobromide Ar 2 SbBr [Ar = 2-(Me 2 NCH 2 )C 6 H 4 ] with Mg in THF gave the distibane Ar 2 Sb-SbAr 2 , which was converted in situ into (Ar 2 Sb) 2 E [E = O (57), S (58)] by air oxidation or treatment with elemental sulfur, respectively (Scheme 18)[51]. Sulfide 58 was also obtained from Ar 2 SbCl with an excess amount of Na 2 S in water/toluene.…”

12-Chloro-6-cyclohexyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine

“…For general background, see: Yin et al (2008); Chovancová et al (2009); Opris et al (2009); Svoboda et al (2010); Tan & Zhang (2011). For related structures, see: Kakusawa et al (2006); Xia et al (2010).…”