机译:氟离子诱导的硅氧和硅硫键与六价氟代三氮磷的反应-硫/含氧单氮杂磷的合成,反应性和X射线结构分析
; fw = 303.11, a = 9.501(2) Angstrom, b = 9.764(3) Angstrom, c = 11.092(5) Angstrom, alpha = 74.97 degrees, beta = 88.03 degrees, gamma = 85.85 degrees, V = 991.0(6) Angstrom(3), and Z = 2. N3P3F4[SCH2CH2CH2S] (4) is orthorhombic, Fdd2; fw = 317.14, a = 18.238(4) Angstrom, b = 41.390(8) Angstrom, c = 5.965(12) Angstrom, V = 4503(2) Angstrom(3), and Z = 16. The P-31 NMR spectra of these derivatives show a large dependence on the ring size and an attempt is made to explain this observation on the basis of structural parameters. Reactions of N3P3F6 With disiloxanes such as (Me(3)SiOCH(2)CH(2))(2)O at temperatures below 80 degrees C yield only the dangling product 5a. When the reaction temperature is elevated to similar to 110 degrees C, an oily liquid that is identified as the bridged fluorophosphazene (N3P3F5OCH2CH2)(2)O (5b) is isolated. When [Me(3)SiOC(CF3)(2)]2C6F4 acts as a bifunctional reagent, a totally fluorinated bridged phosphazene, [N3P3F5OC(CF3)(2)]2C6F4 (6), forms at similar to 65 degrees C. Aromatic disiloxanes are very facile reagents for the formation of spirocyclic products when N2P3F6 is reacted under mild conditions with the bis(trimethylsilyl) ethers of 1,2-catechol, 3-fluoro-1,2-catechol, 2,3-naphthaienediol, and 2,2'-biphenol. No ring degradation is observed with 3-F-1,2-C6H3(OSiMe(3))(2) and 1,2-C6H4(OSiMe(3))(2), which give the monospiro derivatives N3P3F4[3-F-1,2-C6H4O2] (7) and N3P3F4[1,2-C6H4O2] (8a) in good yields as well as the dispirophosphazene derivative N3P3F2[1,2-C6H4O2](2) (8b). Crystals of 8a are orthorhombic Imma; fw = 319.03, a = 7.4642(5) Angstrom, b = 9.5108(7) Angstrom, c = 16.2807(12) Angstrom, V = 1155.78(14) Angstrom(3), and Z = 4; 8b is monoclinic, P2(1); fw = 389.12, a = 10.015 (10) Angstrom, b = 5.612(10) Angstrom; c = 27. 818(4) Angstrom, beta = 96.70 degrees, V = 1552.8(4) Angstrom(3), Z = 4. N3P3F4[2,3-C10H6O2] (9a) is monoclinic, P2(1)/c; fw = 369.09, a = 11.291(2) Angstrom, b = 17.139(3) Angstrom, c = 7.183(10) Angstrom, beta = 101.68 degrees, V = 1361.2(4) Angstrom(3), Z = 4; N3P3F4[2,2'-Cl2H8O2] (10) is monoclinic C2/c; fw = 395.12, a = 24.932(5) Angstrom, b = 7.930(10) Angstrom; 18.875(4) Angstrom, beta = 124.55 degrees, V = 3073.6(10) Angstrom(3), Z = 8. The residual fluorine atoms on the phosphazene rings in 7, 8a, 9a, and 10 can be substituted by fluorophenoxy groups on reaction with the corresponding o-, m-, or p-(trimethylsilyl)phenoxy ether to give fully substituted phosphazenes of the type N(3)P(3)X(OC6H4F)(4) [X = 3-F-1,2-C6H3O2 (11), 1,2-C6H4O2 (12), 2,3-C10H6O2 (13-15), and 2,2'-C12H8O2 (16-18)]. Crystals of N3P3[2,2'-C12H8O2](p-FC6H4O)(4) (18) are triclinic
; fw = 763.49, a = 10.597(2) Angstrom, b = 12.121(2) Angstrom, c = 15.324(3) Angstrom, alpha = 70.38 degrees, beta = 84.53 degrees, gamma = 65.77 degrees, V = 1688.6(5) Angstrom(3), and Z = 2. The N3P3 core in 18 is distorted and the two biphenoxy rings are twisted at 46.1 degrees. [References: 50]
; fw = 303.11,a = 9.501(2)埃,b = 9.764(3)埃,c = 11.092(5)埃,alpha = 74.97度,beta = 88.03度,γ= 85.85度,V = 991.0(6)埃(3),并且Z = 2。N3P3F4 [SCH2CH2CH2S](4)是正交的,Fdd2; fw = 317.14,a = 18.238(4)埃,b = 41.390(8)埃,c = 5.965(12)埃,V = 4503(2)埃(3),Z =16。P-31NMR光谱这些衍生物中的一部分显示出对环尺寸的很大依赖性,并且试图根据结构参数来解释该观察结果。 N3P3F6与二硅氧烷如(Me(3)SiOCH(2)CH(2))(2)O的反应在低于80摄氏度的温度下仅产生悬空产物5a。当反应温度升高至接近110摄氏度时,将分离出一种油状液体,该液体被识别为桥连的氟代磷腈(N3P3F5OCH2CH2)(2)O(5b)。当[Me(3)SiOC(CF3)(2)] 2C6F4充当双功能试剂时,全氟化桥连磷腈[N3P3F5OC(CF3)(2)] 2C6F4(6)的形成类似于65摄氏度。当N2P3F6在温和的条件下与1,2-邻苯二酚,3-氟-1,2-邻苯二酚,2,3-萘二醇和2的双(三甲基甲硅烷基)醚反应时,二硅氧烷是形成螺环产物的非常容易的试剂,2'-双酚。使用3-F-1,2-C6H3(OSiMe(3))(2)和1,2-C6H4(OSiMe(3))(2)观察不到环降解,得到单螺衍生物N3P3F4 [3-F -1,2-C6H4O2](7)和N3P3F4 [1,2-C6H4O2](8a)以及双螺磷腈衍生物N3P3F2 [1,2-C6H4O2](2)(8b)。 8a的晶体是正交晶体的伊玛; fw = 319.03,a = 7.4642(5)埃,b = 9.5108(7)埃,c = 16.2807(12)埃,V = 1155.78(14)埃(3),并且Z = 4。 8b是单斜晶,P2(1)/ n; fw = 389.12,a = 10.015(10)埃,b = 5.612(10)埃; c =27。818(4)埃,β= 96.70度,V = 1552.8(4)埃(3),Z =4。N3P3F4[2,3-C10H6O2](9a)是单斜晶系,P2(1)/ c ; fw = 369.09,a = 11.291(2)埃,b = 17.139(3)埃,c = 7.183(10)埃,β= 101.68度,V = 1361.2(4)埃(3),Z = 4; N3P3F4 [2,2'-Cl2H8O2](10)为单斜C2 / c; fw = 395.12,a = 24.932(5)埃,b = 7.930(10)埃; 18.875(4)埃,β= 124.55度,V = 3073.6(10)埃(3),Z = 8.7、8a,9a和10中磷腈环上的残留氟原子可以被氟苯氧基取代与相应的邻,间或对(三甲基甲硅烷基)苯氧基醚反应,得到类型为N(3)P(3)X(OC6H4F)(4)的完全取代的磷腈[X = 3-F-1, 2-C6H3O2(11),1,2-C6H4O2(12),2,3-C10H6O2(13-15)和2,2'-C12H8O2(16-18)]。 N3P3 [2,2'-C12H8O2](p-FC6H4O)(4)(18)的晶体是三斜晶
; fw = 763.49,a = 10.597(2)埃,b = 12.121(2)埃,c = 15.324(3)埃,alpha = 70.38度,beta = 84.53度,γ= 65.77度,V = 1688.6(5)埃(3),Z =2。18中的N3P3核变形,两个双苯氧基环以46.1度扭曲。 [参考:50]
Phosphorus-nitrogen-compounds; Cyclophosphazenes;
机译:氟离子诱导的硅氧和硅硫键与六价氟代三氮磷的反应-硫/含氧单氮杂磷的合成,反应性和X射线结构分析
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