dibromotris(dimethylphenylphosphine)[hydrazido(2-)]tungsten(IV) | 58081-44-0

• 英文名称: dibromotris(dimethylphenylphosphine)[hydrazido(2-)]tungsten(IV)
• 英文别名: cis,mer-[WBr2(NNH2)(PMe2Ph)3]；cis,mer-[WI2(NNH2)(PMe2Ph)3]
• CAS: 58081-44-0；69610-32-8
• 化学式: C₂₄H₃₅Br₂N₂P₃W
• 分子量: 788.135
• InChiKey: CDEGCSVDFHAKQJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  dibromotris(dimethylphenylphosphine)[hydrazido(2-)]tungsten(IV) 在 pyridine 作用下， 以 吡啶 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  质子化和配体交换由二氮杂物形成的钼和钨的Hydrazido（2-）-络合物

  摘要：

  许多新的肼基（2-）络合物[MX 2（NNH 2）（PMe 2 Ph）3 ]（A; M = Mo或W，X = Cl，Br或I）和反式-[MX（NNH 2）（PMe 2 Ph）4 ] X（B； M = W）是通过将浓HX与顺式[M（N 2）2（PMe 2 Ph）4 ]在甲醇中反应制得的。将各种配体L加到配合物（A）中得到一系列以下类型的配合物：（B：M ＝ Mo或W），当L ＝ PMe 2 Ph时；（B：M ＝ Mo或W）。（C），[MX（NNH 2）（PMe 2 Ph）3当L ＝各种吡啶碱或二甲基甲酰胺时，L] X；（D），[M（NNH 2）（喹）（PMe 2 Ph）3 ] X，当L ＝喹啉8-羟基离子（喹）时；特别是当M ＝ W且X ＝ Br时，[WBr（NNH 2）（S 2 CNMe 2）（PMe 2 Ph）2 ]（L ＝ S 2 CNMe 2）。通过处理顺式-[W（N 2）2-（PMe

  DOI：

  10.1039/dt9780001766
• 作为产物：
  描述：

  cis-{tungsten(dinitrogen)2(P(methyl)2Ph)4} 、 氢溴酸 生成 dibromotris(dimethylphenylphosphine)[hydrazido(2-)]tungsten(IV)
  参考文献：
  名称：

  Synthesis and Reactivities of Pyrrolylimido Complexes of Molybdenum and Tungsten: Formation of Pyrrole and N-Aminopyrrole from Molecular Nitrogen

  摘要：

  Hydrazido(2-) complexes trans-[MX(NNH2)(dppe)(2)](+) (M = Mo, W; X = F, Cl; dppe = Ph(2)PCH(2)CH(2)PPh(2)) and cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X = Cl, Br), which are readily derived from trans-[M(N-2)(2)(dppe)(2)] (1) and cis-[W(N-2)(2)(PMe(2)Ph)(4)] by protonation, condensed with 2,5-dimethoxytetrahydrofuran to afford pyrrolylimido complexes of the type trans-[MX(NNCH=CHCH=CH)(dppe)(2)](+) (3(+)) and cis,mer-[WX(2)(NNCH=CHCH=CH)(PMe(2)Ph)(3)] (6), respectively. Their structures were characterized spectroscopically and further confirmed by X-ray diffraction study. Electrophilic substitution reactions at the pyrrole ring in complexes 3(+) occurred selectively at the beta-position to give the corresponding beta-substituted pyrrolylimido complexes trans- [MX(NNCH=C(E)CH=CH)(dppe)(2)](+) (E Br, CN, SO3-, COR), although only chlorination of 3(+) with N-chlorosuccinimide in THF took place predominantly at the a-position. This beta-regioselectivity is in sharp contrast to the a-regioselectivity of free pyrrole and is probably caused by the steric effect of the dppe ligands. Complexes 3(+) were readily reduced under ambient conditions with LiAlH4 to liberate pyrrole and N-aminopyrrole in high yields. Further, the tetrahydrido complexes [MH(4)(dppe)(2)], which can be converted back into the original dinitrogen complexes 1, were recovered in moderate yields after the reduction. This accomplishes the synthetic cycle for pyrrole and N-aminopyrrole starting from the dinitrogen complexes 1. beta-Heptylpyrrole was also prepared by starting from 3c(+) (M = W, X = Cl) by the beta-selective heptanoylation followed by the reduction with LiAlH4. On the other hand, reduction of 6b (X = Br) with LiAlH4 predominantly produced pyrrole, whereas treatment of 6b with KOH/EtOH liberated N-aminopyrrole in a high yield.

  DOI：

  10.1021/ja00154a019

文献信息

• Selective N–N and W–N Bond Cleavage of Tungsten Pyrrolylimido Complexes Derived from Tungsten Dinitrogen Complex
  作者：Takao Sasagawa、Hidetake Seino、Youichi Ishii、Yasushi Mizobe、Masanobu Hidai

  DOI：10.1246/bcsj.72.425

  日期：1999.3

  [WBr2(NNCH=CHCH=CH)(CNBut)(PMe2Ph)2] ) with LiAlH4 followed by methanolysis gave pyrrole and ammonia in almost quantitative yields. On the other hand, 1-aminopyrrole was quantitatively produced from the complexes by the reaction of KOH in alcohol when L = CO, PhC≡CH, or PhCHO. While analogous treatment of 6 with KOH in ethanol afforded both pyrrole and 1-aminopyrrole with low selectivity under N2 atmosphere, 1-aminopyrrole

  [WX2(NNCH=CHCH=CH)(L)(PMe2Ph)2] ) (X = Cl, Br, I; L = PMe2Ph (6), CNBut, CO, PhC≡ CH、PhCHO、Br) 与 LiAlH4 或 KOH 产生吡咯、1-氨基吡咯和氨，其中反应条件和配体 L 的性质对吡咯/1-氨基吡咯的选择性有显着影响。因此，用LiAlH4还原顺，反-([WBr2(NNCH=CHCH=CH)(CNBut)(PMe2Ph)2])，然后进行甲醇分解，以几乎定量的产率得到吡咯和氨。另一方面，当 L = CO、PhC≡CH 或 PhCHO 时，通过 KOH 在醇中的反应从配合物中定量产生 1-氨基吡咯。虽然在乙醇中用 KOH 对 6 进行类似处理，在 N2 气氛下以低选择性得到吡咯和 1-氨基吡咯，1-氨基吡咯在 1 个大气压的 CO 下以极好的收率由 6 生产。相反，吡咯和氨是由 6b (X = Br)
• Synthesis and Structures of Tungsten (1-Pyridinio)imido Complexes and Their Facile N−N Bond Cleavage¹
  作者：Hiroshige Ishino、Shin'ichi Tokunaga、Hidetake Seino、Youichi Ishii、Masanobu Hidai

  DOI：10.1021/ic981116n

  日期：1999.5.1

  The tungsten (1-pyridinio)imido complexes [WX(2)(NNC(5)H(4)OMe)(L)(PMe(2)Ph)(2)](+), [WX(2)(NNC(5)H(2)Me(3))(L)(PMe(2)Ph)(2)](+), and [WCl(2)NNC(5)H(2)(COOEt)(2)Ph}(L)(PMe(2)Ph)(2)](+) (X = Cl, Br; L = CO, C(2)H(4), PMe(2)Ph) were synthesized by the reaction of the salts of pyrylium cations with the hydrazido complexes [WX(2)(NNH(2))(L)(PMe(2)Ph)(2)], which were derived from the dinitrogen complex cis-[W(N(2))(2)(PMe(2)Ph)(4)]. The complexes obtained were characterized by spectroscopic measurements as well as crystallographic studies of cis,mer-[WBr(2)(NNC(5)H(4)OMe-4)(PMe(2)Ph)(3)][PF(6)], cis, trans-[WCl(2)(NNC(5)H(4)OMe-4)(CO)(PMe(2)Ph)(2)][ClO(4)], cis, trans- [WCl(2)(NNC(5)H(2)Me(3)-2,4,6)(CO)(PMe(2)Ph)(2)][OTf] (OTf = OSO(2)CF(3)), and cis,trans-[WCl(2)(NNC(5)H(4)OMe-4)(C(2)H(4))(PMe(2)Ph)(2)][ClO(4)], which revealed that the N-N bond distances of these (1-pyridinio)imido complexes are shorter than those of the trialkyl- or unsubstituted hydrazidium complexes so far reported. The (1-pyridinio)imido complexes with a pi-acidic ligand (CO or C(2)H(4)) undervent smooth N-N bond cleavage on reaction with cobaltocene under ambient conditions to liberate the pyridines in moderate to high yields. In some reactions that were conducted in the presence of HNEt(3)-Cl, the corresponding imido (NH) complexes were recovered as the metal products. The (1-pyridinio)imido complexes also reacted with KOH in MeOH to give the pyridines and ammonia in high yields. These reactions provide the first examples of N-N bond cleavage of well-defined hydrazidium complexes and accomplish the synthesis of pyridines from molecular nitrogen under mild conditions.
• Synthesis and Structure Determinations of Complexes Containing a Five-Membered Lactam Structure Based on Organohydrazido(2−) Ligands¹
  作者：Hidetake Seino、Youichi Ishii、Masanobu Hidai

  DOI：10.1021/ic960778e

  日期：1997.1.1

  Acid-catalyzed reactions of the hydrazido(2-) complexes cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X=Cl, Br) with phthalaldehyde gave the (phthalimidin-2-yl)imido complexes cis,mer-[WX(2)(NNCH2C6H4CO)(PMe(2)Ph)(3)], via the condensation of the terminal NH2 group with one of the formyl groups and the following cyclization to form a phthalimidine ring. Crystal structure of the chloro complex 3a was unambiguously determined by X-ray analysis. Reaction of 3a with HBr liberated the (phthalimidin-2-yl)imido ligand as 2-aminophthalimidine in moderate yield, while treatment of 3a with KOH in THF selectively cleaved the N-N bond to give phthalimidine. A similar condensation of the hydrazido(2-) complex trans-[WF(NNH2)(dppe)(2)](+) (8a(+); dppe=Ph(2)PCH(2)CH(2)PPh(2)) with phthalaldehyde resulted in the formation of the diazoalkane complex trans-[WF(NN=CHC6H4CHO)(dppe)(2)](+). However, further treatment of the latter complex with AlCl3 afforded the corresponding (phthalimidin-2-yl)imido complex trans-[WF(NNCH2C6H4CO)(dppe)(2)](+). When 8a(+) and its molybdenum analogue were reacted with 2,5-dimethoxy-2,5-dihydrofuran in the presence of a catalytic amount of acid, trans-[M(NNCH=CHCH2CO)(dppe)(2)](+) (11(+); M=Mo, W) was formed as the kinetic product, which gradually isomerized to the thermodynamically more stable compound trans-[MF(NNCH2CH=CHCO)(dppe)(2)](+) (12(+)). Both 11(+) and 12(+) (M=W) were crystallographically characterized, and the mechanism for the isomerization of 11(+) to 12(+) was proposed based on the results of the H-1 NMR measurements.