lithium;oxolane;phenylphosphanide | 149752-71-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: lithium;oxolane;phenylphosphanide
• CAS: 149752-71-6
• 化学式: C₄H₈O*C₆H₆P*Li
• 分子量: 188.135
• InChiKey: LUBQZIXYURFPBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.74
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二氯二茂锆 、 lithium;oxolane;phenylphosphanide 以 四氢呋喃 为溶剂， 以30%的产率得到(η(5)-C5H5)2 (1,2,3-triphenyltriphosphane-1,3-diyl)zirconocene(IV)
  参考文献：
  名称：

  Ho, Jianwei; Breen, Tricia L.; Ozarowski, Andrzej, Inorganic Chemistry, 1994, vol. 33, # 5, p. 865 - 870

  摘要：

  DOI：

文献信息

• Hey, Evamarie; Bott, Simon G.; Atwood, Jerry L., Chemische Berichte, 1988, vol. 121, p. 561 - 564
  作者：Hey, Evamarie、Bott, Simon G.、Atwood, Jerry L.

  DOI：——

  日期：——
• Formation and reactivity of the early metal phosphides and phosphinidenes Cp*2Zr:PR, Cp*2Zr(PR)2, and Cp*2Zr(PR)3
  作者：Zhaomin Hou、Tricia L. Breen、Douglas W. Stephan

  DOI：10.1021/om00032a044

  日期：1993.8

  The reactions Of CP*2ZrCl2 with 2 equiv of LiPHPh led to the formation of the unstable species CP*2Zr(PHPh)2 (1), which yields CP*2Zr(PPh2) (2) on standing for 1 h and a third product CP*2Zr(PPh)3 (3) which appears after 1 week. The compound 3 is derived cleanly from mixtures of 1 and 2 by addition of excess PH2Ph. In the related reactions, CP*2ZrCI2 reacts with 2 equiv of LiPH(C6H2Me3) to give the wine-red diphosphido-species CP*2Zr(PH(C6H2Me3))2 (4). This compound converts slowly to ortho-metalation product CP*2Zr(CH2C6H2Me2PH) (5) and the species CP*2Zr(PC6H2Me3)2 (6). These reactions infer terminal phosphinidene intermediates. Such an intermediate can be intercepted via reaction of 4 with MeCN affording CP*2Zr(NCMe)2P(C6H2Me3) (7). Further evidence for the intermediacy of a phosphinidene complex is derived from the reaction Of CP*2ZrCI2 and LiPH(C6H2Me3) in DME where the species CP*2Zr(P(C6H2Me3))(Cl)Li(DME) (8) is observed. A bent terminal phosphinidene derivative CP2Zr(P(C6H2t-BU3))(PMe3) (9) (Zr=PR, 2.505(4) angstrom) is isolated from the reaction Of CP2ZrCl2 with Li(PH(C6H2t-BU3)) in the presence of PMe3. While the phosphinidene intermediate affords the novel phosphametallocycle 7, the species 5, 6, and 3 also act as synthons for unprecedented phospha-, diphospha-, and triphosphametallocycles. Compound 5 reacts with MeCN and benzaldehyde to effect insertion of the organic reagents into the Zr-P bonds yielding the phosphametallocycles CP*2Zr(CH2C6H2Me2PH(C(Me)N)) (10) and Cp*2Zr(CH2C6H2Me2PH(C(Ph)O)) (11), respectively, while similar reactions of compound 6 afford the 1,2-diphosphametallocycles CP*2Zr(NC(Me)PC6H2Me3)2 (12) and CP*2Zr(OCH(Ph)PC6H2Me3)2 (13). Compound 12 reacts with NH4Cl affording CP*2ZrCI(NC(Me)P(C6H2Me3)PH(CrH2Me3)) (14). Cleavage of the Zr-P bonds in compound 6 is effected by sequential acidolysis with HCCPh affording CP*2Zr(CCPh)(P(C6H2Me3)PH(C6H2Me3)) (15) and CP*2Zr(CCPh)2(16), while reaction of 6 with acetone gives the dienolate complex Cp*2Zr(OC(Me)CH2)2 (17) and reaction of 6 with CH2I2 affords CP*2ZrI2 (18). Compound 3 acts as synthon for new 1,2,3-triphosphametallocycles as reactions of 3 with MeCN and benzaldehyde afford CP*2Zr(NC(Me))(PPh)3 (19) and CP*2Zr(OCH(Ph))(PPh)3 (20), respectively. The chemistry of these Zr-P species offers synthetic routes to a variety of unprecedented phosphametallocycles which augurs well for metal-mediated synthesis of organophosphorus compounds. The formulations of a number of these compounds have been confirmed crystallographically. These data are summarized as follows: 6, P2(1)/n, a = 11.464(3) angstrom, b = 19.140(5) angstrom, c = 16.165(5) angstrom, beta = 90.93(3)-degrees, V = 3546(3) angstrom3, Z = 4; 9, P2(1)/c, a = 15.011(5) angstrom, b = 9.824(5) angstrom, c = 21.745(5) angstrom, beta = 103.21(3)-degrees, V = 3122(2) angstrom3, Z = 4; 11, P2(1)/c, a = 19.352(6) angstrom, b = 10.444(8) angstrom, c = 19.647(12) angstrom, beta = 109.20(3)-degrees, V = 3750(4) angstrom3, Z = 4; 13, P2(1)/c, a = 21.301(7) angstrom, b = 10.478(4) angstrom, c = 25.102(7) angstrom, beta = 111.75(2)-degrees, V = 5204(3) angstrom3, Z = 4; 14, P2(1)/n, a = 14.731(11) angstrom, b = 17.401(5) angstrom, c = 17.143(9) angstrom, beta = 113.83(5)-degrees, V = 4020(4) angstrom3, Z = 4; 15, P2(1)2(1)2(1), a = 14.572(10) angstrom, b = 28.618(12) angstrom, c = 11.084(6) angstrom, V = 4622(4) angstrom3, Z = 4; 19, P1BAR, a = 12.634(4) angstrom, b = 17.690(4) angstrom, c = 10.169(4) angstrom, alpha = 103.43(2)-degrees, beta = 113.66(2)-degrees, gamma = 82.00(2)-degrees, V = 2022(1) angstrom3, Z = 2.