Preparation and crystal structures of five organoantimony halides; (p-tolyl)antimony(III) dichloride and dibromide, diphenylantimony(III) bromide, 2′-diyl)antimony(III) chloride and bis-(2′-chlorobiphenyl-2-yl)antimony(V) trichloride

Millington, Peter L.; Sowerby, D. Bryan

doi:10.1016/0022-328x(94)87123-x

Cited by 41 publications

(18 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Bei den vergleichenden Untersuchungen fiel auf, daû in der homologen Reihe der Halogendiphenylstibane (1) lediglich die Kristallstruktur des Chlor-Derivates noch unbekannt war, obwohl gerade dieser Verbindung aufgrund ihrer Stellung zwischen dem im Festko È rper u È ber nahezu symmetrische Fluorbru È cken zu Ketten assoziierten Fluordiphenylstiban [13] und den praktisch ohne spezifische intermolekulare Wechselwirkungen kristallisierenden Abko È mmlingen der schwereren Halogene [3,14] besondere Bedeutung zukommt. Da Chlordiphenylstiban (1 d) im Rahmen pra È-parativer Untersuchungen ohnehin verfu È gbar war, wurde seine noch ausstehende Struktur am Einkristall bestimmt und zur Analyse der Moleku È lpackung mit einer Reihe von Verbindungen a È hnlichen Formeltyps (Schema 1) verglichen.…”

unclassified

“…Bereits mehr als zehn Jahre zuvor hatten Cotton und Kibala [31] bei Umsetzungen von Triphenylphosphan mit u È berschu È ssigem Diiod die Verbindung {[(H 5 C 6 ) 3 P±I] 2 I 3 } + I 3 ± aus Dichlormethan und das Isomer [(H 5 C 6 ) 3 P±I] + I 3 ± aus Toluol isolieren sowie etwa gleichzeitig du Mont, Pohl u. a. [32] die Struktur des Adduktes [(H 3 C) 3 C] 3 P ® I±I aufkla È ren ko È nnen. Z. Anorg.…”

unclassified

See 1 more Smart Citation

Untersuchungen am Chlordiphenyl- und Tribenzylstiban sowie am Tribenzyldibromstiboran - Molekülstrukturen und Isotypie

Becker

Mündt

Sachs

et al. 2001

Z. anorg. allg. Chem.

View full text Add to dashboard Cite

Professor Josef Goubeau in memoriamInhaltsu È bersicht. Chlordiphenylstiban (1 d) {P2 1 /c; Z = 4; a = 1191,8(1); b = 853,4(1); c = 1112,0(1) pm; b = 93,60(1)°; ±100 ± 2°C} kristallisiert isotyp zu einer Reihe homologer Verbindungen der Zusammensetzung (H 5 C 6 ) 2 E±X (E = As, X = Cl, Br, I; E = Sb, X = Br, I); der Strukturtyp des Tribenzylstibans (5 d) {Pbca; Z = 8; a = 832,1(2); b = 2681,3(5); c = 1600,9(3) pm; ±100 ± 3°C} ist vom Tribenzylmethanol, -silanol und -silan her bekannt. Demgegenu È ber weist Tribenzyldibromstiboran (6) {P2 1 /n; Z = 4; a = 938,4(2); b = 2292,4(5); c = 1019,7(2) pm; b = 112,71(1)°; ±100 ± 3°C} keine entsprechenden Beziehungen zu bereits bekannten Strukturtypen auf. Charakteristische, gemittelte Bindungsla È ngen und -winkel sind {1 d: Sb±Cl 240,9(1); Sb±C 214,0 pm; Cl±Sb±C 93,8; C±Sb±C 98,6(1)°; 5 d: Sb±C 217,5(3) pm; C±Sb±C 94,9(6)°; 6: Sb±Br 264,6; Sb±C 217,0(8) pm; Br±Sb±Br 179,4(1)°; C±Sb±C 120°; Br±Sb±C 84,8(2)°bis 94,7(2)°}. Beim Stiboran 6 deuten sich sehr schwache intermolekulare Antimon´´Brom-Wechselwirkungen (Sb´´Br 417 pm) an; sie wirken sich jedoch in auffallender Weise auf die Moleku È lkonformation aus. Element±Element Bonds. X. Studies of Chloro(diphenyl)stibane, Tribenzylstibane and Tribenzyldibromostiborane ± Molecular Structures and Isotypism Abstract. Chlorodiphenylstibane (1 d) {P2 1 /c; Z = 4; a = 1191.8(1); b = 853.4(1); c = 1112.0(1) pm; b = 93.60 (1)°; ±100 ± 2°C} crystallizes isotypically with a series of homologous (H 5 C 6 ) 2 E±X compounds (E = As, X = Cl, Br, I; E = Sb, X = Br, I); the structure type of tribenzylstibane (5 d) {Pbca; Z = 8; a = 832.1(2); b = 2681.3(5) pm; c = 1600.9(3); ±100 ± 3°C} is already known from tribenzylmethanol, -silanol and -silane. Tribenzyldibromostiborane (6) {P2 1 /n; Z = 4; a = 938.4(2); b = 2292.4(5); c = 1019.7(2) pm; b = 112.71(1)°; ±100 ± 3°C} does not show an analogous relationship to known structure types. Characteristic mean bond lengths and angles are {1 d, Sb±Cl 240.9(1), Sb±C 214.0 pm, Cl±Sb±C 93.8°, C±Sb±C 98.6(1)°; 5 d, Sb±C 217.5(3) pm, C±Sb±C 94.9(6)°; 6, Sb±Br 264.6; Sb±C 217.0(8) pm, Br±Sb±Br 179.4(1)°; C±Sb±C 120°; Br±Sb±C 84.8(2)°to 94.7(2)°}. Stiborane 6 exhibits very weak intermolecular Sb´´Br interactions of 417 pm which, however, affect the molecular conformation in a striking way.

show abstract

unclassified

Untersuchungen am Chlordiphenyl- und Tribenzylstiban sowie am Tribenzyldibromstiboran - Molekülstrukturen und Isotypie

Becker

Mündt

Sachs

et al. 2001

Z. anorg. allg. Chem.

View full text Add to dashboard Cite

show abstract

“…1 H-and (4) (1) 17) and bromodi(p-tolyl)stibane 34) were prepared according to the reported procedures. Chiral HPLC analysis was carried out on a Shimadzu HPLC 10A with a UV-VIS detector using a Chiralcel OB (0.46 cmϫ25 cm) made by Daicel Chemical Industries Ltd. AMSb (2) To a solution of 1 (1.49 g, 10 mmol) in ether (15 ml) was added n-BuLi (7.2 ml, 11 mmol, 1.52 mol/l in hexane) at 0°C under an argon atmosphere, and the solution was stirred for 24 h at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Optically Active Organoantimony Compounds Having an (S)-.ALPHA.-Methylbenzyldimethylamine Group and Its Evaluation for Asymmetric Reaction.

Yasuike

Okajima

Kurita

2002

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

The chemistry of asymmetric catalysts is an interesting research field in asymmetric reactions and has recently been the focus of attention.1) A number of chiral ligands containing nitrogen, 2) phosphorus [3][4][5][6][7][8][9] and arsenic [10][11][12][13] have been widely studied and are well documented. With respect to enantiomerically pure phosphine ligands bearing a chiral benzylamine moiety, (R/S)-[a-methyl-2-(diphenylphosphino)-benzyl]dimethylamine (AMPhos) [14][15][16][17] and its (h 6 -arene)-chromium complex 18,19) have been reported to be effective chiral ligands for enantioselective reductions, cross-coupling reactions, and allylic alkylations. It is also known that a variety of optically active phosphine derivatives bearing a ferrocene skeleton can be used in a wide range of asymmetric reactions.7) However, the synthesis of optically active organoantimony compounds and its applications to asymmetric reactions have not been reported so far. In this context, we are interested in the synthesis and utilization of optically active organoantimony compounds for asymmetric synthesis and have recently reported an efficient and stereoselective resolution of racemic Sb-chiral stibindoles 20) and 2,2Ј-bis[di(p-tolyl)stibano]-1,1Ј-binaphthyls (BINASb).21) Here we report the syntheses of new, optically active antimony compounds having a C-chiral benzylamine moiety, (S)-(amethyl-2-di-p-tolylstibanobenzyl)dimethylamine [AMSb] (2) and AMSb-Cr(CO) 3 complex (4), and their use for transition metal-catalyzed enantioselective hydrosilylation of ketones.The syntheses of the optically pure organoantimony compounds 2 and 4 used in this study are shown in Chart 1. (S)-(a-Methylbenzyl)dimethylamine (1) was ortho-lithiated with n-butyllithium (n-BuLi) in ether according to the literature method, 17) followed by trapping with bromodi(p-tolyl)stibane [(p-Tol) 2 SbBr] to give AMSb (2) in 45% yield; [a] D ϩ12.6°( cϭ2, CHCl 3 ). On the other hand, (h 6 -arene)chromium complexes have some significant properties owing to the strong electron-withdrawing ability and steric bulkiness of the coordinated transition metal, and their applications to organic synthesis have been developed.22) It is also known that the arylic hydrogens on the chromium complexes are easily lithiated to functionalize at an appropriate position. The key common starting (S)-tricarbony[h 6 -(a-methylbenzyl)dimethylamine]chromium (3) was obtained by the reaction of 1 with hexacarbonylchromium in 73% yield as yellow crystals. 23)The novel chiral antimony compound 4 was readily prepared by way of diastereoselective lithiation of 3. According to the procedure reported by Gibson and co-workers, 24) the chromium complex 3 was lithiated by treatment with tertbutyllithium (t-BuLi) in anhydrous diethyl ether at Ϫ80°C under an argon atmosphere. Subsequent treatment of the mixture with (p-Tol) 2 SbBr at the same temperature gave rise to CHCl 3 ) as the sole product. The planar chirality of the (h 6 -arene)chromium moiety is deduced to be R from diastereoselective ortho-lithi...

show abstract

“…Although there has been recent interest in the structures of a range of arylantimony(III) halides, including SbPhX2, where X = CI, Br or I (Mundt, Becker, Stadelmann & Thurn, 1992), SbArX2, where Ar = 4-tolyl and X = CI or Br, and SbPh2Br (Millington & Sowerby, 1994), structural information for related As compounds is limited to results from film data for the isostructural diphenylarsenic chloride (Trotter, 1962a), bromide (Trotter, 1962b) and iodide (Trotter, o1963). For the iodide, only the As--I distance (2.53 A) was reported.…”

Section: Commentmentioning

confidence: 99%

“…As there are no reports of accurate structure determinations for any diorganoarsenic halides, perhaps the most useful comparison is with diphenylantimony bromide (Millington & Sowerby, 1994), where the same order of bond angles is observed but, because of the greater size of antimony, the C--Sb---C angle is reduced to 98.5 (3) ° and the C--Sb---Br angles to 93.5 (2) and 95.3 (2) °.…”

Section: #-~ C10mentioning

confidence: 99%

Diphenylarsenic(III) Iodide

Begley¹,

Sowerby²,

Silaghi‐Dumitrescu³

1995

Acta Crystallogr C

View full text Add to dashboard Cite

Preparation and crystal structures of five organoantimony halides; (p-tolyl)antimony(III) dichloride and dibromide, diphenylantimony(III) bromide, 2′-diyl)antimony(III) chloride and bis-(2′-chlorobiphenyl-2-yl)antimony(V) trichloride

Cited by 41 publications

References 17 publications

Untersuchungen am Chlordiphenyl- und Tribenzylstiban sowie am Tribenzyldibromstiboran - Molekülstrukturen und Isotypie

Untersuchungen am Chlordiphenyl- und Tribenzylstiban sowie am Tribenzyldibromstiboran - Molekülstrukturen und Isotypie

Synthesis of Optically Active Organoantimony Compounds Having an (S)-.ALPHA.-Methylbenzyldimethylamine Group and Its Evaluation for Asymmetric Reaction.

Diphenylarsenic(III) Iodide

Contact Info

Product

Resources

About