CHEMICAL-REDUCTION OF A PENTASTANNA[1.1.1]PROPELLANE DERIVATIVE AND THE SYNTHESIS AND MOLECULAR-STRUCTURE OF A BICYCLO[1.1.1]PENTASTANNANE

被引：36

作者：

SITA, LR ^{[1
]}

KINOSHITA, I ^{[1
]}

机构：

[1] CARNEGIE MELLON UNIV,DEPT CHEM,PITTSBURGH,PA 15213

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 24期

关键词：

D O I：

10.1021/ja00180a027

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cyclic voltammetry of 2,2,4,4,5,5-hexakis(2,6-diethylphenyl)pentastanna[1.1.1 Jpropellane(3) in THF shows two quasireversible one-electron reduction waves at E1/2 = -1.41 and -1.93 V (V vs NHE) which correspond to the [3]/[3]- and the [3]-/[3]2- redox couples, respectively. Chemical reduction of 3 with 0.5% potassium amalgam can be achieved in the presence of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (abbreviated as crypt) to produce the radical anion complex [3]-[K, crypt]+. This radical anion has been characterized by ESR which shows giso = 1.92, a(119/117Sn1,3) = 15 G, and a(119/117Sn2,4,5) = 57 G for the isotropic spectrum at 410 K and g舔 = 1.99 and g⊥ = 1.89 for the anisotropic frozen spectrum at 130 K. Compound 3 quantitatively reacts with methyl iodide to produce 2,2,4,4,5,5-hexakis(2,6-diethylphenyl)-1-iodo-3-methylbicyclo[1.1.1]pentastannane (4), which can be isolated as deep-red crystals. Single crystals of 4 are, at 20 °C, monoclinic, space group P21c-C2h5 (No. 14) with a = 14.785 (2) Å, b = 20.319 (3) Å, c = 22.951 (3) Å, ° = 97.63 (1)°, V = 6834 (2) Å3, and Z = 4. The tin-tin bond lengths between the bridging and bridgehead tin atoms of 4 are in the range of 2.825 (1) to 2.842 (1) Å, and the distance between the two bridgeheadtin atoms is 3.361 (1) Å. The results of these investigations support the view that the central bridgehead-bridgehead bonding interaction of 3 contributes very little to the stability of this system. © 1990, American Chemical Society. All rights reserved.

引用

页码：8839 / 8843

页数：5

共 16 条

[1]

Minkin V.I., Minyaev R.M., Zhdanov Y.U.A., Nonclassical Structures of Organic Compounds, MIR Publishers, (1987)

[2]

Wiberg K.B., Chem. Rev., 89, (1989)

[3]

Schleyer P.V.R., Janoschek R., Angew. Chem., Int. Ed. Engl., 26, (1987)

[4]

Nagase S., Kudo T., Organometallics, 6, (1987)

[5]

Schoeller W.W., Dabisch T., Busch T., Inorg. Chem., 26, (1987)

[6]

Nagase S., Kudo T., Kurakake T., J. Chem. Soc., Chem. Commun., (1988)

[7]

Kitchen D.B., Jackson J.E., Allen L.C., J. Am. Chem. Soc., 112, (1990)

[8]

Nagase S., Kudo T., Organometallics, 7, (1988)

[9]

Wiberg K.B., Bader R.F.W., Lau C.D.H., J. Am. Chem. Soc., 109, (1987)

[10]

Sita L.R., Bickerstaff R.D., J. Am. Chem. Soc., 111, (1989)

← 1 2 →