Synthesis, Structure, and Reactivity of Intramolecularly Coordinated Organoantimony and Organobismuth Sulfides

Abstract

Organoantimony(III) and organobismuth(III) sulfides, containing O,C,O-chelating ligands (L1−3 = 2,6-(ROCH2)2C6H3 −, where R = Me (L1), t-Bu (L2), or mesityl (L3)), [L1−3MS]2, where M = Sb (L1 (5), L2 (6), L3 (7)) or M = Bi (L2 (8)), were prepared by the reaction of parent organoantimony and organobismuth chlorides with Na2S·9H2O in toluene/water. All sulfides 5−8 were characterized by elemental analysis, electrospray ionization mass spectrometry, 1H and 13C NMR spectroscopy, and X-ray diffraction techniques. Organoantimony sulfides 5−7 are stable both in solution and in the solid state in contrast to the organobismuth congener, which is stable at −30 °C but decomposes at ambient temperature. While the reaction of 5 and 7 with I2 yielded the expected organoantimony iodides L1,3SbI2 (L1 (9), L3 (10)), compound 6 containing ligand L2 gives the unexpected oxastibol 12 besides the intended diiodide L2SbI2 (11). The molecular structure of 12 in the solid state was determined by X-ray diffraction techniques and showed formation of an Sb−O covalent bond as a result of C−O ether bond cleavage.

Structural analysis of organometallic compounds with soft ionization mass spectrometry

“…As (Larsen et al, 2001) B (Dostál et al, 2007c) Bi (Dostál et al, 2006a;Dostál et al, 2007c;Dostál et al, 2009b;Fridrichová et al, 2009;Chovancová et al, 2009) Co (Arrais et al, 2006) Cr and Fe (Martinez-Alvarez et al, 2004) Cr and Ru (Moret et al, 2005) Fe and Ru (Paim et al, 2005) Ge (Jirásko et al, 2009; Mo (Gun et al, 2003) Os (Dorcier et al, 2005;Dorcier et al, 2008;Schmid et al, 2007) Pb (Casas et al, 2004) Pd (Macchioni et al, 2003) Rh (Dorcier et al, 2008) Ru (Ang et al, 2006;Dorcier et al, 2005;Dorcier et al, 2008;Schmid et al, 2007) Se (Zhou et al, 2007) Sb (Dostál et al, 2006a;Dostál et al, 2007a;Dostál et al, 2007c;Dostál et al, 2008;Dostál et al, 2009a;Dostál et al, 2009b;Fridrichová et al, 2009;Chovancová et al, 2009;Machuča et al, 2007) Sn (Baul et al, 2005a;Baul et al, 2005b;Baul et al, 2005c;Baul et al, 2006a;Baul et al, 2006b;Baul et al, 2006c;Baul et al, 2006d;Baul et al, 2007a;Baul et al, 2007b;…”

“…As (Florencio et al, 1997;Pedersen & Francesconi, 2000); Au (Dinger & Henderson, 1998a, b;Goss et al, 2003;Kilpin et al, 2007); Bi (Dostál et al, 2009b;Chovancová et al, 2009); Co (Alsberg et al, 2001); Fe (Henderson & Alley, 2002;KaneMaguire et al, 1996;Seiwert & Karst, 2007;Wu et al, 2008); Ge Takeuchi et al, 2006;; Hg (Nicholson & Whitley, 2004); Pb (Casas et al, 2004); Pd (Chevrin et al, 2007);…”

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

“…Recently, Dostál and co-workers synthesized and structurally characterized monoarylantimony dihalides containing OCO pincer ligands 99a-c, 100a-b and 101a-b [22,61,84]. The 99a-c dichlorides were prepared via the lithiation of appropriate OCO pincer ligands with n-BuLi and subsequent reaction with SbCl 3 (Scheme 32).…”

“…Treatment of the chlorides 99a-c and Na 2 S in toluene/water resulted in the formation of the corresponding organoantimony(III) sulfides 107a-c (Scheme 37) [84]. The single-crystal XRD analysis of sulfides 107a-c revealed that all three compounds are centrosymmetric dimmers with a planar central 4-membered Sb 2 S 2 ring.…”

Synthesis and Structural Study of Triphenylbismuth Bis (Salicylate)

“…However, the utilization of organobismuth compounds trivalent and pentavalent for organic synthesis is rarely reported partly due to the unstable nature of the Bi-C bonds [6,7]. Recent developments show that the incorporation of a bulky substituent in pentavalent organobismuth complex can result of organobismuth compounds that have stable Bi-C bonds [8][9][10]. In our research group, we have been working on the synthesis of stable pentavalent organobismuth compounds.…”