Methyldixanthogenatostibane

Abstract

Inhaltsübersicht. Methyldixanthogenatostibane CHgSb(S2CORh erhält man entweder durch Reaktion von Methyldibromstiban mit entsprechenden Natriumxanthogenaten bei tiefen Temperaturen (-78°C) oder durch Einschiebung von CS 2 in Methyldialkoxistibane. Die Röntgenstrukturanalyse von CHaSb(S2COC2H5h zeigt, daß Im Kristall die Chelatliganden das Antimonatom intraund intermolekular koordinieren, so daß eine pentagonal-pyramidale bzw. unter Einbezug des freien Elektronenpaars pentagonal-bipyramidale Koordination am Antimon vorliegt. Methyldixanthatostibanes Abstract. Methyldi:x:anthatostibanes CHaSb(S2COR)2 are obtained either byreacting sodium xanthates with methyldibromostibanes at low temperatures (-78°0) or by insertion of CS 2 in methyldialkoxistibanes. An X-ray analysis of CHaSb(S2COC2H5)2 is given. It shows that in the crystal the Sb atom is chelated fivefold-inter and intramolecular-by sulfur atoms, so that a pentagonal pyramidal or pentagonal bipyramidal, with inclusion the lone pair, geometry is observed.

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…Similar structures were reported by Wieber et al, who prepared [{Cp(CO) 2 Fe}Bi(SCSOMe) 2 ] and [{Cp(CO) 2 Fe}Bi(S 2 CNEt 2 ) 2 ], the latter containing two four-membered rings based around the bismuth atom [56]. Mono-iron species have also been reported for the dibromo-, diiodo-, and dimethylbismuth analogues [5,53,56]. The related trimetal species [Cp(CO)(Me 3 P)Fe(BiMe 2 )] 2 Mo(CO) 4 was prepared by Malisch in 1983, by the reaction of [{Cp(CO)(PMe 3 )Fe}BiMe 2 ] with the norbornadiene molybdenum carbonyl complex (Scheme 4) [57].…”

“…Similar structures were reported by Wieber et al, who prepared [{Cp(CO) 2 Fe}Bi(SCSOMe) 2 ] and [{Cp(CO) 2 Fe}Bi(S 2 CNEt 2 ) 2 ], the latter containing two four-membered rings based around the bismuth atom [56]. Mono-iron species have also been reported for the dibromo-, diiodo-, and dimethylbismuth analogues [5,53,56].…”

Creating Iron– and Rhenium–Bismuth Bonds by Reactions with Organometallic Hydrides

“…Compounds containing Fe–Bi bonds, have been accessed in the past by different routes, which are briefly exemplified here focussing on bismuthanes bearing a bismuth atom linked via a Fe–Bi bond to organoiron fragments, such as the well‐known η 5 ‐cyclopentadienyl dicarbonyl iron anion [Fp – = ( η 5 ‐C 5 H 5 )(CO) 2 Fe – ]. Two routes to compounds like [{( η 5 ‐C 5 H 4 R )(CO) 2 Fe}BiMe 2 ] ( R = H), [{( η 5 ‐C 5 H 4 R)(CO) 2 Fe} 2 Bi X ] ( R = H, X = Cl, Br; R = Me, X = Cl) and [{( η 5 ‐C 5 H 4 R )(CO) 2 Fe} 3 Bi] ( R = H, Me) have been established so far: (i) salt metathesis reactions treating bismuth halides with alkali metal salts of [Fp] – [27–30] or (ii) cleavage of the Fe–Fe bond in the [Fp 2 ] dimer in reactions with bismuth halides or bismuth dithiocarbamates as first reported by Cullen and co‐workers in 1971 for the synthesis of [FpBiCl 2 ] and later for the synthesis of [FpBi X 2 ] [ X = SC(S)NEt 2 , SC(S)OMe] by Wieber and co‐workers . The latter approach was recently successfully adapted by Mehring and co‐workers to access [Fp R BiBr 2 ] {Fp R = Fp; Fp t Bu [( η 5 ‐C 5 H 3 ‐1,3‐ t Bu 2 )(CO) 2 Fe]; Fp* [( η 5 ‐C 5 Me 5 )(CO) 2 Fe]} starting from [Fp R 2 ] and BiBr 3 (Scheme ) and also by us to synthesize the carboxylates [FpBi(O 2 C R ) 2 ] 2 via reaction of [Fp 2 ] with [Bi(O 2 CR) 3 ] [ R = H ( VII ), CH 3 ( VIII ), t Bu ( IX )] (Scheme ) .…”

Bis(ethylxanthato)phenylantimony(III)

“…Comparisons can be made with the following structures: Sb(SzCOEt)3 (Gottardi, 1961;Hoskins, Tiekink & Winter, 1985), containing asymmetrically chelating ligands [Sb--S 2.511 (2) and 3.002 (3),~] related by a threefold axis, but no short intermolecular contacts; SbMe(S2COEt)2 (Wieber, Wirth & Burschka, 1983), again containing asymmetrically chelating ligands [Sb---S 2.581 (2)/2.834 (2) and 2.617 (2)/2.904 (2) A] and, as in (1), an intermolecular Sb...S contact [3.353 (2)~,], which raises the antimony coordination number to six and links the molecules into infinite chains; the dithiocarbamate SbMe(S2CNEt2)2 (Wieber, Wirth, Metter & Burschka, 1985), which has a similar structure [Sb---S 2.554 (2)/2.960 (2) and 2.538 (2)/2.904 (2) ,~], but the intermolecular contacts [Sb--.S 3.847 (2) A] are much weaker, giving loose dimers in the solid; and SbPh[SzP(Oipr)2] (Gupta, Rai, Mehrotra, Jain, Hopkins & Tiekink, 1985), which contains independent molecules and again asymmetrically chelating lig oands [Sb--S 2.516 (3)/3.056 (2) and 2.529 (3)/3.067 (3) A].…”