Dimethyl‐tellur‐bis(alkylxanthogenate)

Abstract

Inhaltsü bersi cht. Man erhält Dimethyl-telIur-bis(alkylxanthogenate) des Typs R2Te(S2COR'lz mit R = CH 3 , sowie R' = CH s , C 2 H s , i-C s H 7 durch Umsetzung von Dimethyltellur-diiodid mit den stöchiometrischen Mengen der jeweiligen Natriumxanthogenate.Ebemalls führt eine Einschiebung von CS 2 in die Te-O-Bindung von Dimethyl-tellur-bis(alkoxyden) zu den Dimethyl-tellur-bis(alkylxanthogenaten). Die Röntgenstrukturanalyse von (CH3hTe(S2COCH3)2 zeigt, daß das Molekül im Kristall als V'-pentagonale Bipyramide vorliegt. Tellurium -Dimethyl-bis (alkylxanthates)Abstract. Tellurium dimethyl-bis(alkylxanthates) of the type R2Te(S2COR')2 with R = CH 3 and R ' = CH 3 , C 2 H 5 , i-C s H 7 are obtained by reaction of tellurium dimethyldiiodide with freshly prepared sodium xanthates. Another preparative method is the insertion of CS 2 in tellurium dimethylbis(alkoxydes). The X-ray analysis of (CH3)2Te(S2COCHsh shows, that in the crystal the moleculc has a IjJ-pentagonal bipyramidal configLlration around tellurium. Allgemeiner TeilOrganotellurxanthogenate des zweiwertigen Tellurs sind schon seit längerem bekannt und wurden erstmals von Foss 1952 synthetisiert und untersucht [1, 2J. Vom vierwertigen Tellur sind bisher nur einige wenige Dithiocarbamate des Typs RTe(S2CNR2'h und R2Te(S2CNR2')2 mit R = Alk., Aryl; R' = Alk. publiziert worden [3, 4J. TeIV-Xanthogenat-Verbindungen sind bislang nicht bekannt. Im Rahmen unserer Untersuchungen über Xanthogenate von Organometallaten der schwereren Va-Elemente Sb und Bi [5,6,12] sollte versucht werden, dabei gewonnene Erfahrungen auf ein Element der 6. Hauptgruppe, nämlich das Tellur, zu über-tragen. Von besonderem Interesse war dabei a) wie sich dieses Element in seiner mittleren Oxydationsstufe IV gegenüber dem Reduktionsmittel Xanthogenat verhält und b) wie die Substitution eines R-M:::]M = Sb, Bi) durch RzTe:::::: -Restes sich auf die strukturellen Eigenschaften der Verbindungen auswirken würde.Darstellung. Zur Synthese von Dimethyl-tellur-bis(alkylxanthogenaten) stehen zwei Reaktionswege offen.

Synthesis, spectroscopic, and structural studies of dimethyltellurium(IV) alkylene and diphenyl dithiophosphates. Crystal structures of and

“…(32) and it has been proposed that it constitutes a secondary intermolecular interaction (15). A similar phenomenon was noted for R,TeCl, where one Te-Cl bond was much longer than the other and it too appeared to be the only one involved in any intermolecular association (33).…”

“…This suggests that the second sulfur atom of these anisobidentate ligands could be included in the coordination sphere around tellurium. This was the approach taken for Me,Te[S,COMe], (15) and Ph,Te[S,P(OEt),], (13) in which the two Te--S intramolecular secondary interactions, 3.303(1) and 3.352(1) A in the former and 3.367(2) and 3.353(3) A in the latter, were included and the structures were described as a pseudo-pentagonal bipyramid and a bi-capped trigonal bipyramid, respectively, rather than as the pseudo-trigonal bipyramid formed by the closest atoms. The same trigonal bipyramidal arrangement occurs in C,H,Te[S,P(OEt),], (10) but it was described as an eight coordinate linear polymer because in addition to the two For personal use only.…”

Synthesis, spectroscopic characterization of O,O-alkylene dithiophosphates of tellurolane and 1-oxa-4-tellurane. Single crystal structures of C4H8Te[S2P(OCH2)2CMe-nPr]2 and C4H8OTe[S2P(OCH2)2CEt2]2

“…(2) Å for 3, in this compound one of the bonds is significantly longer than the other, as was also found for Me 2 Te-[S 2 P(OCMe 2 ) 2 ] 2 , Me 2 Te[S 2 P(OCH 2 ) 2 CEt 2 ] 2 [15] and Ph 2 Te[S 2 P(OCH 2 ) 2 CMe 2 ] 2 [18]. The S-Te-S bond angles are of 174.61(10)°and 174.08(8)°, so that deviation from 180°is slightly less than in the dimethyltellurium xanthate and dithiocarbamate derivatives Me 2 Te[SCOMe] 2 [28] and Me 2 Te[S 2 CNMe 2 ] 2 [7] where the angles are 165.90(3)°and 166.5(1)°, respectively, and comparable to those reported for analogous non-cyclic dithiophosphates derivatives Ph 2 Te[S 2 P(OMe) 2 ] 2 [10] and Ph 2 Te[S 2 P(OEt) 2 ] 2 [8]. Table 3 presents some comparative values. There are two longer secondary intramolecular Te-S interactions: Te(1)-S(2) 3.495 Å for 2 and Te(1)-S(2) 3.380 and 3.381 Å for 3, respectively, these are substantially shorter than the sum of the van der Waals radii of 3.86 Å [27].…”

Synthesis, spectroscopic and structural studies of O-methyl and O-isopropyl monothiocarbonate (monoxanthate) derivatives of dimethyl-and diphenyltellurium(IV). Crystal structures of Me2Te[SCO2(i-Pr)]2, Ph2Te[SCO2(i-Pr)]2, Me2TeCl[SCO2Me], and Me2TeBr[SCO2(i-Pr)]

“…9. The lack of Te--Br interactions is surprising because in Me,TeBr, there are two intermolecular interactions with Te--Br distances of 3.560 (4) and 3.661 (4) A, which are associated with the longer of the two Te-Br bonds, and in Ph,TeBr, the closest such interaction reported is 3.93 (39), yet the shortest secondary Te--Br contact in 8 of 4.833 (2) A is considerably longer than the sum of the van der Waals radii. Te--X associations are extensive and in, for example, a series of R,TeCI, compounds with different R groups (36,38,(40)(41)(42), Te--Cl interactions are consistently found (43), with the exception of (9-BrC6H,),TeC1, where Te--Br interactions of 3.71 and 3.80 A replace those expected for Te--Cl (43).…”

“…There have been a number of reports on the reactions of organotellurium(1V) compounds with a variety of 1,l -dithio ligands, such as O-alkyl dithiocarbonates (1)(2)(3)(4)(5)(6), N,N-dialkyl dithiocarbamates (5)(6)(7)(8)(9)(10)(11)(12)(13)(14), and 0,O-dialkyl(alky1ene) dithiophosphates (4-6, [14][15][16][17][18][19][20][21], as well as a recent extensive review of supramolecular associations in tellurium complexes with sulfur ligands (22). In general, the chemistry of monothio ligands has received much less attention but a few reports have appeared relating to main group element derivatives including those on monothiocarbamate compounds of thallium (23), tin (24,25), and, most recently, tellurium (26) as well as on monothiophosphate compounds of tin (27,28).…”