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O,O-Alkylene dithiophosphate derivatives of halodimethyltellurium(IV) of the type where X = Cl, Br, I, G = −CMe2CMe2−, −CH2CMe2CH2−, and −CH2CEt2CH2−, were synthesized in 80−90% yields by the react...

Dimethylbis(pyrrolidyl and piperidyl dithioformato)tellurium(IV) compounds and the corresponding halodimethyl compounds, Me2TeX[S2CN(CH2)nCH2], where n = 3, 4 and X = Cl, Br, and I, have been prepa...

A series of new complexes, Mo2O2S2[S2P(OR)2]2 (where R = Et, n-Pr, i-Pr) and Mo2O2S2[S2POGO]2 (where G = −CH2CMe2CH2−, −CMe2CMe2−) have been prepared by the dropwise addition of an ethanolic solution of the ammonium or sodium salt of the appropriate O,O-dialkyl or -alkylene dithiophosphoric acid, or the acid itself, to a hot aqueous solution of molybdenum(V) pentachloride. The complexes were also formed by heating solutions of Mo2O3[S2P(OR)2]4 or Mo2O3[S2POGO]4 species in glacial acetic acid. The Mo2O2S2[S2P(OR)2]2 and Mo2O2S2[S2POGO]2 compounds were characterized by elemental analyses, 1H, 13C, and 31P NMR, and infrared and Raman spectroscopy, as were the 1:2 adducts formed on reaction with pyridine. The crystal structures of Mo2O2S2[S2P(OEt2)]2, Mo2O2S2[S2P(OEt)2]2·2NC5H5, and Mo2O3[S2P(OPh)2]4 were determined. Mo2O2S2[S2P(OEt)2]2 (1) crystallizes in space group C2/c, No. 15, with cell parameters a = 15.644(3) A, b = 8.339(2) A, c = 18.269(4) A, β = 103.70(2)°, V = 2315.4(8) A3, Z = 4, R = 0.0439, and R...

O-Alkyl dithiocarbonate (xanthate) derivatives of halodimethyltellurium(IV), Me2TeX[S2COR], where R = Me, Et, and i-Pr and X = Cl, Br, and I, have been prepared in 75−88% yields by the reaction of the potassium salt of the appropriate dithiocarbonic acid with dimethyltellurium dihalide in equimolar ratio. The compounds were characterized by infrared, Raman, and 1H, 13C, and 125Te NMR spectroscopy. The crystal structures of Me2TeCl[S2COEt] (2) and Me2TeI[S2CO(i-Pr)] (9) were determined. Me2TeCl[S2COEt] (2), which crystallizes in the monoclinic space group P21/a (No. 14), has the cell parameters a = 9.583(2) A, b = 10.264(3) A, c = 22.502(2) A, β = 97.86(1)°, V = 2192.4(8) A3, and Z = 8, and Me2TeI[S2CO(i-Pr)] (9), which crystallizes in the triclinic space group P1 (No. 2), has the cell parameters a = 11.332(5) A, b = 11.83(2) A, c = 10.19(2) A, α = 94.8(2)°, β = 105.53(7)°, γ = 85.10(7)°, V = 1309(3) A3, and Z = 2. The immediate environment about tellurium in both molecules can be described as that of a s...

The S-alkyl trithiocarbonate (trixanthate) derivatives Me 3 Ge[S 2 CSR], Ph 3 Ge[S 2 CSR], and Ph 2 Ge[S 2 CSR] 2 , where R=Et, i-Pr, n-Pr, and n-Bu, have been prepared in 73-85% yields by the reaction of the potassium salt of the appropriate trithiocarbonic (trixanthic) acid with iodotrimethylgermane, bromotriphenylgermane, or dichlorodiphenylgermane. The compounds were characterized by infrared, Raman, and 1 H and 13 C NMR spectroscopy. The crystal structure of Ph 2 Ge(S 2 CS(i-Pr)] 2 was determined, and it crystallizes in space group P1 (No. 2) with the cell parameters a=10.752(9) A, b=13.36(1) A, c=9.64(2) A, α=105.8(1) o , β=113.2(1) o , γ=91.79(9) o , V=1211(3) A 3 , and Z=2; R=0.0638, and R w =0.0626

The tetrakis(O-alkyl dithiocarbonato)germanium derivatives Ge[S 2 COMe] 4 , Ge[S 2 COEt] 4 , and Ge[S 2 CO(i-Pr)] 4 have been prepared in 55-65% yields by reaction of the sodium salt of the dithiocarbonic (xanthic) acid with tetrachlorogermane. The compounds were characterized by infrared, Raman, and 1 H and 13 C NMR spectroscopy.

The O-alkyl dithiocarbonate (xanthate) derivatives PhGe[S 2 CO(i-Pr)] 3 , Ph 2 Ge[S 2 CO(i-Pr)] 2 , Ph 3 Ge[S 2 CO(i-Pr)], Ph 3 Ge-[S 2 COMe], Ph 3 Ge[S 2 COEt], Ph 3 Ge[S 2 CO(n-Bu)], Ph 2 Ge[S 2 CO(n-Bu)] 2 , and possibly PhGe[S 2 COR] 3 , where R=Me, and Et, have been prepared in 60-86% yields by reaction of the sodium or potassium salt of the dithiocarbonic (xanthic) acid with trichlorophenyl-, dichlorodiphenyl- or chlorotriphenylgermane. The compounds were characterized by elemental analysis and infrared, Raman and 1 H and 13 C NMR spectroscopy

Dimethylbis(pyrrolidyl and piperidyl dithioformato)tellurium(IV) compounds and the corresponding halodimethyl compounds, Me(2)TeX[S(2)CN(CH(2))(n)()CH(2)], where n = 3, 4 and X = Cl, Br, and I, have been prepared. The compounds were characterized by elemental analysis and IR, Raman, and multinuclear NMR spectroscopies, including some variable temperature studies. The following crystallize as monoclinic in space group P2(1)/c (No. 14). Me(2)Te[S(2)CN(CH(2))(3)CH(2)](2) (1): a = 6.38(1) Å, b = 18.902(7) Å, c = 14.672(6) Å, beta = 97.73(6) degrees V = 1752(2) Å(3), Z = 4, R = 0.0636, R(w) = 0.0642. Me(2)Te{[S(2)CN(CH(2))(3)CH(2)][S(2)CN(CH(2))(4)(CH(2))]} (3): a = 6.55(1) Å, b = 19.716(6) Å, c = 14.900(9) Å, beta = 95.27(8) degrees, V = 1928(3) Å(3), Z = 4, R = 0.0618, R(w) = 0.0511. Me(2)TeCl[S(2)CN(CH(2))(3)CH(2)] (4): a = 9.952(3) Å, b = 6.386(3) Å, c = 18.834(3) Å, beta = 95.32(2) degrees, V = 1191.7(6) Å(3), Z = 4, R = 0.0358, R(w) = 0.0314. Me(2)TeBr[S(2)CN(CH(2))(3)CH(2)] (5): a = 10.085(4) Å, b = 6.446(4) Å, c = 19.020(5) Å, beta = 95.08(3) degrees, V = 1231.7(8) Å(3), Z = 4, R = 0.0559, R(w) = 0.0469. Me(2)TeCl[S(2)CN(CH(2))(4)CH(2)] (7) is P2(1)/a (No. 14) with a = 9.756(2) Å, b = 11.242(2) Å, c = 12.028(3) Å, beta = 92.26(3) degrees, V = 1318.2(7) Å(3), Z = 4, R = 0.0438, R(w) = 0.0442, and Me(2)TeI[S(2)CN(CH(2))(4)CH(2)] (9) is P2(1) (No. 4) with a = 6.019(3) Å, b = 8.986(4) Å, c = 13.012(2) Å, beta = 100.61(3) degrees, V = 691.7(6) Å(3), Z = 2, R = 0.0364, R(w) = 0.0305. Me(2)TeI[S(2)CN(CH(2))(3)CH(2)] (6) is orthorhombic in Pbca (No. 61) with a = 13.951(6) Å, b = 19.849(8) Å, c = 9.261(4) Å, V = 2564(1) Å(3), Z = 8, R = 0.0392, R(w) = 0.0326, and Me(2)Te[S(2)CN(CH(2))(4)CH(2)](2) (2) is triclinic in Ponemacr; (No. 2) with a = 9.624(2) Å, b = 12.904(3) Å, c = 9.008(2) Å, alpha = 98.29(2) degrees, beta = 111.19(2) degrees, gamma = 99.64(2) degrees, V = 1002.5(4) Å(3), Z = 2, R = 0.0504, R(w) = 0.0454. The immediate environment about Te is that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. The second sulfur atom appears also to be in the coordination sphere resulting in the following distorted arrangements about Te: pseudo pentagonal bipyramidal in 1 and 3, octahedral in 2, and square pyramidal in 5, 6, 7, and 9.

A series of new complexes, Mo(2)O(2)S(2)[S(2)P(OR)(2)](2) (where R = Et, n-Pr, i-Pr) and Mo(2)O(2)S(2)[S(2)POGO](2) (where G = -CH(2)CMe(2)CH(2)-, -CMe(2)CMe(2)-) have been prepared by the dropwise addition of an ethanolic solution of the ammonium or sodium salt of the appropriate O,O-dialkyl or -alkylene dithiophosphoric acid, or the acid itself, to a hot aqueous solution of molybdenum(V) pentachloride. The complexes were also formed by heating solutions of Mo(2)O(3)[S(2)P(OR)(2)](4) or Mo(2)O(3)[S(2)POGO](4) species in glacial acetic acid. The Mo(2)O(2)S(2)[S(2)P(OR)(2)](2) and Mo(2)O(2)S(2)[S(2)POGO](2) compounds were characterized by elemental analyses, (1)H, (13)C, and (31)P NMR, and infrared and Raman spectroscopy, as were the 1:2 adducts formed on reaction with pyridine. The crystal structures of Mo(2)O(2)S(2)[S(2)P(OEt(2))](2), Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2).2NC(5)H(5), and Mo(2)O(3)[S(2)P(OPh)(2)](4) were determined. Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2) (1) crystallizes in space group C2/c, No. 15, with cell parameters a = 15.644(3) Å, b = 8.339(2) Å, c = 18.269(4) Å, beta = 103.70(2) degrees, V = 2315.4(8) Å(3), Z = 4, R = 0.0439, and R(w) = 0.0353. Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2).2NC(5)H(5) (6) crystallizes in space group Ponemacr;, No. 2, with the cell parameters a = 12.663(4) Å,b = 14.291(5) Å, c = 9.349(3) Å, alpha = 100.04(3) degrees, beta = 100.67(3) degrees, gamma = 73.03(3) degrees V = 1557(1) Å(3), Z = 2, R = 0.0593, and R(w) = 0.0535. Mo(2)O(3)[S(2)P(OPh)(2)](4) (8) crystallizes in space group P2(1)/n, No. 14, with cell parameters a = 15.206(2)Å, b = 10.655(3)Å, c = 19.406(3)Å, beta = 111.67(1) degrees, V = 2921(1)Å(3), Z = 2, R = 0.0518, R(w) = 0.0425. The immediate environment about the molybdenum atoms in 1 is essentially square pyramidal if the Mo-Mo interaction is ignored. The vacant positions in the square pyramids are occupied by two pyridine molecules in 6, resulting in an octahedral environment with very long Mo-N bonds. The terminal oxygen atoms in both 1 and 6 are in the syn conformation. In 8, which also has a distorted octahedral environment about molybdenum, two of the dithiophosphate groups are bidentate as in 1 and 6, but the two others have one normal Mo-S bond and one unusually long Mo-S bond.

(Me 3 SiCH 2 SeMe) 2 PdCl 2 cristallise dans le systeme orthorhombique, groupe Pbca et sa structure est affinee jusqu'a R=0,0249•(Me 3 GeCH 2 SeMe) 2 PtCl 2 cristallise egalement dans Pbca avec R=0,0431. La configuration, pyramidale autour du selenium, est plan carre autour du palladium ou du platine