PENTACOORDINATED MOLECULES .35. STRUCTURES OF MIXED-LIGAND SULFUR-CONTAINING SPIROCYCLIC PHOSPHORANES

被引:26
作者
DAY, RO [1 ]
SAU, AC [1 ]
HOLMES, RR [1 ]
机构
[1] UNIV MASSACHUSETTS, DEPT CHEM, AMHERST, MA 01003 USA
关键词
D O I
10.1021/ja00508a016
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Single-crystal X-ray analysis of the sulfur-containing spirocyclic phosphorane (CH3C6H3S2)(C|4H8O2)PPh (111) revealed a geometry only slightly displaced from a rectangular pyramid. The X-ray analyses of the related thio spirocyclics, (C6H4OS)2PPh (IV) and (C6H4S2)2PPh (V), showed geometries closer to the idealized trigonal pyramid. Ill crystallizes in the monoclinic space group P21n, with a = 9.816 (2) Å, b = 14.047 (2) Å, c = 16.857 (3) Å, ² = 100.19 (1)°, and Z = 4. IV crystallizes in the monoclinic space group P21/c, with a = 9.042 (4) k, b = 10.119 (4) Å, c = 18.787 (4) Å, (3 = 96.63 (3)°, and Z = 4. V crystallizes in the monoclinic space group P21/n, with a = 16.701 (4) Å, b = 6.638 (1) Å, c = 16.994 (2) Å, ² = 114.29(2)°, and Z = 4. Data for all three compounds were collected, using an automated Enraf-Nonius CAD4 diffractometer, out to a maximum 2ΘMoKα of 55°. Full-matrix least-squares refinement techniques led to the final agreement factors of R = 0.043, Rw= 0.048 for III based on the 3171 reflections having 1≥2σ, R = 0.034, Rw= 0.043 for IV for the 3025 reflections having I > 2σ1, and R = 0.030 and Rw= 0.037 for V for the 2980 reflections having I > 2σ. The specific geometries obtained for III and IV are related to the different placement of the ring sulfur and oxygen atoms that constitute an identical set in each of the two structures. It is concluded that the general structural principles formulated for spirocyclic oxyphosphoranes thus far appear to apply to the related sulfur derivatives. © 1979, American Chemical Society. All rights reserved.
引用
收藏
页码:3790 / 3801
页数:12
相关论文
共 27 条
[11]   SOLVOLYSIS OF METHYL OS-ETHYLENE PHOSPHOROTHIOATE [J].
GAY, DC ;
HAMER, NK .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1972, (08) :929-&
[12]  
GAY DC, 1970, CHEM COMMUN, P1564
[13]  
Gillespie R. J., 1972, MOL GEOMETRY
[14]   CONFORMATIONAL PREFERENCES OF PENTACOORDINATE SPIROCYCLIC PHOSPHORUS-COMPOUNDS [J].
HOLMES, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (13) :4143-4149
[16]   STRUCTURAL DISTORTIONS OF CYCLIC PHOSPHORANES AND BERRY EXCHANGE COORDINATE - QUANTITATIVE DESCRIPTION [J].
HOLMES, RR ;
DEITERS, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (10) :3318-3326
[17]   CONFORMATIONAL ENERGY CALCULATIONS ON 5-MEMBERED RINGS IN PENTACOORDINATE PHOSPHORUS [J].
HOLMES, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (19) :5379-5385
[18]  
HOLMES RR, ACS175 MON
[19]   PENTACOORDINATED MOLECULES .30. CRYSTAL AND MOLECULAR-STRUCTURES OF SYMMETRICAL DIOXADIAZASPIROPHOSPHORANES CONTAINING PHOSPHORUS-HYDROGEN BONDS [J].
MEUNIER, PF ;
DAY, RO ;
DEVILLERS, JR ;
HOLMES, RR .
INORGANIC CHEMISTRY, 1978, 17 (11) :3270-3276
[20]   STEREOCHEMISTRY OF PHOSPHORUS(V) FLUORIDES [J].
MUETTERTIES, EL ;
SCHMUTZLER, R ;
MAHLER, W .
INORGANIC CHEMISTRY, 1963, 2 (03) :613-&