| 153818-37-2

• CAS: 153818-37-2
• 化学式: C₁₉H₄₈Cl₂OP₂Si₄Zr
• 分子量: 629.009
• InChiKey: MAZUMNIXOIZHKD-IJRZPAASSA-L

反应信息

• 作为产物：
  描述：

  在 CO 作用下， 以 四氢呋喃 为溶剂， 生成 、
  参考文献：
  名称：

  锆与膦甲甲烷配体的配合物：合成，反应性和X射线结构测定

  摘要：

  The reactions of ZrCl4 with lithium phosphinomethanides were investigated. With LiCH2-PMe2, 1, and Li[CH(PMe2)2], 2, the products could not be characterized satisfactorily. With {(TMEDA)Li[CH(PMe2)(SiMe3)]}2, 3, a mixture of compounds Cl(4-n)Zr[CH(PMe2)(SiMe3)]n (n = 1-4), 4a-d, was obtained and characterized spectroscopically. Various coordination modes of the phosphinomethanide ligands are observed for n = 3 (4c) and n = 4 (4d) by means of NMR spectroscopy. With (TMEDA){Li[C(PMe2)(SiMe3)2]}2, 5, only disubstitution is observed, and Cl2Zr[C(PMe2)(SiMe3)2]2, 6, containing hexacoordinated Zr, was isolated in high yield as red crystals (monoclinic, C2/c, with a = 9.273(1) angstrom, b = 15.078(2) angstrom, c = 22.062(2) angstrom, beta = 95.09(1)degrees, Z = 4, wR = 0.025). Complex 6 in toluene solution inserts CO into a Zr-C bond, and after a subsequent 1,2-silyl shift a phosphino enolate complex is formed, which dimerizes to give {Cl2Zr[C(PMe2)(SiMe3)2][OC(SiMe3)=C(SiMe3)PMe2]}2, 7(yellow crystals: monoclinic, P2(1)/n, with a = 10.149(1) angstrom, b = 16.503 (2) angstrom, c = 19.307(3) angstrom, beta = 97.13(1)degrees, Z = 2, wR = 0.031). In THF solution 6 also inserts CO, and spectroscopic evidence indicates a mixture of two compounds: the phosphorusylide (Me3Si)(Me3SiO)C=C(PMe2)PMe2=C(SiMe3)2(=L), 8, and LZrCl2, 9. With the lithium diphosphinomethanides (D)Li[C(PR2)2(SiMe3)] (D = -, R = Me, 5a; D = TMEDA, R = Ph, 5b; D = TMEDA, R = Me, 5c), the hexacoordinate complex Cl2Zr[ C(PMe2)2(SiMe3)]2, 10, and the ionic species [(TMEDA)2Li]{Cl3Zr[C(PR2)2(SiMe3)]2}, 11 (R = Ph) and 12 (R = Me), with heptacoordinated zirconium are obtained, and the latter both were characterized by X-ray structure determinations: 11, red crystals, orthorhombic, Pbca with a = 19.016(2) angstrom, b = 32.385(4) angstrom, c = 23.906(3) angstrom, Z = 8, wR = 0.070; 12.2MePh, red crystals, monoclinic, P2(1)c with a = 16.138(2) angstrom, b = 13.837(1) angstrom, c = 25.779(3) angstrom, beta = 102.19(1)degrees, Z = 4, wR = 0.051.

  DOI：

  10.1021/om00014a036