TOWARD STABILIZING RECTANGULAR-PYRAMIDAL GEOMETRIES IN NONMETALS - POLYCYCLIC PHOSPHORUS ESTERS

被引：10

作者：

DAVIS, RV ^{[1
]}

WINTERGRASS, DJ ^{[1
]}

JANAKIRAMAN, MN ^{[1
]}

HYATT, EM ^{[1
]}

JACOBSON, RA ^{[1
]}

DANIELS, LM ^{[1
]}

WROBLEWSKI, A ^{[1
]}

AMMA, JP ^{[1
]}

DAS, SK ^{[1
]}

VERKADE, JG ^{[1
]}

机构：

[1] IOWA STATE UNIV SCI & TECHNOL,DEPT CHEM,AMES,IA 50011

来源：

INORGANIC CHEMISTRY | 1991年 / 30卷 / 06期

关键词：

D O I：

10.1021/ic00006a032

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The preparation of the novel polycyclic phosphorus compounds Z activated P(OCH2)2CHCHCH2O(CH2OR) and Z activated P(OCH2)2C-(CH2)(x)CCH2O(CH2OR) (Z = lone pair, O, S, Se, BH3, and CPh3+, x = 1-4, and R = H and Z = lone pair, x = 1-4, R = C(O)Ph) are reported. Compounds containing Z = lone pair and R = H were found to undergo an acid-catalyzed rerrangement, yielding the isomeric phosphonates O(H) activated POCH2CHCH2OCH2CHCH2O and O(H) activated POCH2C(CH3)(x)CCH2OCH2CH2O. A possible pathway for this rearrangement is discussed. Over a temperature range of 223-350 K, the compounds possessing a pendant alcohol group (R = H) displayed no tendency to give the corresponding phosphorane even under deprotonating conditions. The molecular structures of (HOCH2)2C(CH2)3C(CH2OH)2, an isomer of O(H) activated POCH2C(CH2)2CCH2OCH2CH2O, Ph3C(O)- activated POCH2C(CH2OH)(CH2)3CCH2O(CH2OH), O activated P(OCH2)2C(CH2)2CCH2O(CH2O)(CH2OH), and O activated P(OCH2)2C(CH2)3CCH2O(CH2OH) determined by X-ray means are presented. Crystallographic parameters for these compounds are space group PBAR1, a = 7.342 (3) angstrom, b = 11.857 (3) angstrom, c = 6.333 (2) angstrom, alpha = 100.47 (3)-degrees, beta = 115.57 (3)-degrees, gamma = 85.51 (4)-degrees, and Z = 2; space group C2/c, a = 11.452 (8) angstrom, b = 6.451 (3) angstrom, c = 26.03 (5) angstrom, beta = 93.03-degrees, and Z = 8; space group P2(1)/c, a = 15.638 (2) angstrom, b = 11.119 (3) angstrom, c = 17.404 (3) angstrom, beta = 106.06 (1)-degrees, and Z = 4; space grou P2(1)/n, a = 7.022 (1) angstrom, b = 10.5157 (9) angstrom, c = 13.122 (2) angstrom, beta = 103.340 (8)-degrees, and Z = 4; and space group P2(1)/c, a = 7.545 (3) angstrom, b = 11.133 (5) angstrom, c = 12.061 (3) angstrom, beta = 91.14 (3)-degrees, and Z = 4, respectively.

引用

页码：1330 / 1341

页数：12