Monothiocarbonate derivatives of diorganotellurium(IV), R2Te[SCO2R′]2, and R2TeX[SCO2R′], where R = Me, Ph; R′ = Me, i-Pr; X = Cl, Br, and I, have been prepared and characterized by vibrational and 1H, 13C, and 125Te NMR spectroscopy. Me2Te[SCO2(i-Pr)]2 (2): P21/n (No. 14) with cell parameters a = 6.942(6) Å, b = 25.599(3) Å, c = 9.404(6) Å, β = 94.48(6)°, V = 1666(1) Å3, Z = 4, R = 0.0648, Rw = 0.0624; Ph2Te[SCO2(i-Pr)]2 (4): P21/n (No. 14) with a = 12.360(4) Å, b = 12.277(3) Å, c = 15.066(3) Å, β = 102.82(2)°, V = 2229.1(9) Å3, Z = 4, R = 0.0368, Rw = 0.0312; Me2TeCl[SCO2Me] (5); P21/c (No. 14) with a = 5.193(2) Å, b = 18.118(4) Å, c = 9.613(5) Å, β = 91.31(6)°, V = 904.2(6) Å3, Z = 4, R = 0.0396, Rw = 0.0361; and Me2TeBr[SCO2(i-Pr)] (8): P21/n (No. 14) with a = 11.701(2) Å, b = 6.250(2) Å, c = 16.152(2) Å, β = 98.43(1)°, V = 1168.4(4) Å3, Z = 4, R = 0.0369, Rw = 0.0325. In all molecules, the immediate environment about tellurium is that of the saw-horse structure in which the lone pair is assumed to be stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. In 2 and 5, the terminal oxygen atoms are oriented toward tellurium, whereas in 4, one O(i-Pr) group is oriented toward tellurium, as it is in 8. In the latter cases, the terminal oxygen atoms act as weak bridges to form a pseudo dimeric species in 4 and a pseudo polymer in 8. Supramolecular interactions in 2 and 5 lead to a sulfur-bridged dimer in the former and a chlorine-bridged polymer in the latter. Key words: structure, tellurium, dimethyl, diphenyl, monothiocarbonates.
二
硫代
碳酸二有机
碲(IV)衍
生物,R
2Te[SCO
2R′]
2,和R
2TeX[SCO
2R′],其中R = Me,Ph;R′ = Me,i-Pr;X = Cl,Br和I,已经制备并通过振动和
1H,
13C和
125Te核磁共振光谱表征。Me
2Te[SCO
2(i-Pr)]
2 (2):P2
1/n (No. 14),晶胞参数a = 6.942(6) Å,b = 25.599(3) Å,c = 9.404(6) Å,β = 94.48(6)°,V = 1666(1) Å
3,Z = 4,R = 0.0648,R
w = 0.0624;Ph
2Te[SCO
2(i-Pr)]
2 (4):P2
1/n (No. 14),a = 12.360(4) Å,b = 12.277(3) Å,c = 15.066(3) Å,β = 102.82(2)°,V = 2229.1(9) Å
3,Z = 4,R = 0.0368,R
w = 0.0312;Me
2TeCl[SCO
2Me] (5);P2
1/c (No. 14),a = 5.193(2) Å,b = 18.118(4) Å,c = 9.613(5) Å,β = 91.31(6)°,V = 904.2(6) Å
3,Z = 4,R = 0.0396,R
w = 0.0361;和Me
2TeBr[SCO
2(i-Pr)] (8):P2
1/n (No. 14),a = 11.701(2) Å,b = 6.250(2) Å,c = 16.152(2) Å,β = 98.43(1)°,V = 1168.4(4) Å
3,Z = 4,R = 0.0369,R
w = 0.0325。在所有分子中,
碲的周围环境是锯马鞍结构,其中孤对电子被认为是立体
化学活性的,并占据一个扭曲的三角双锥体的赤道位置。在2和5中,末端氧原子朝向
碲,而在4中,一个O(i-Pr)基团朝向
碲,就像在8中一样。在后一种情况下,末端氧原子作为弱桥连接形成了4中的伪二聚体物种和8中的伪聚合物。2和5中的超分子相互作用导致前者中的
硫桥二聚体和后者中的
氯桥聚合物。关键词:结构,
碲,二甲基,二苯基,二
硫代
碳酸盐。