(PhMe2P)2Re(N)Cl(S2CNEt2) | 151995-63-0

• 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: (PhMe2P)2Re(N)Cl(S2CNEt2)
• CAS: 151995-63-0
• 化学式: C₂₁H₃₂ClN₂P₂ReS₂
• 分子量: 660.238
• InChiKey: KNQJVHZAPHHDQL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.62
• 重原子数：
  29.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  27.03
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (PhMe2P)2Re(N)Cl(S2CNEt2) 、 silver trifluoromethanesulfonate 、 二甲基苯基磷 以 二氯甲烷-D2 为溶剂， 生成 fac-[(PhMe2P)3Re(N)(S2CNEt2)]OTf
  参考文献：
  名称：

  Kinetic Effects in Heterometallic Dinitrogen Cleavage

  摘要：

  The rhenium(I) dinitrogen complex (PhMe2P)(4)ClRe(N-2) reacts with [Mo-2(S2CNEt2)(6)](OTf)(2) (6) to give the N-2-bridged complex [(PhMe2P)(4)ClRe(mu-N-2) Mo(S2CNEt2)(3)] OTf ([7] OTf). Spectroscopic (v(NN) = 1818 cm(-1)) and structural data [d(NN) = 1.167(6) angstrom] indicate that the bridging N-2 moiety in 7(+) is slightly activated relative to free N-2 or to the mononuclear Re complex. However, the complex is stable with respect to N2 cleavage. The putative products of such a cleavage, the known (Et2NCS2)(3)Mo(N) (5) and the newly prepared [(PhMe2P)(4)ClRe(N)] OTf ([9] OTf), are stable compounds that do not react with each other to give products of nitride coupling. Thus, the failure of 7(+) to interconvert with 5 and 9(+) is due not to the thermodynamic stability of the N N bond but rather to kinetic factors that disfavor N-2 cleavage and nitride coupling. Implications of this result for using polar effects to facilitate N-2 cleavage to nitrides as a strategy for nitrogen fixation are discussed.

  DOI：

  10.1021/ic061153b
• 作为产物：
  描述：

  dichloronitridotris(dimethylphenylphosphine)rhenium(V) 、 sodium diethyldithiocarbamate trihydrate 以 甲醇 为溶剂， 以65%的产率得到(PhMe2P)2Re(N)Cl(S2CNEt2)
  参考文献：
  名称：

  I的混合配体配合物I.ReNCl2（Me2PhP）3与二齿螯合物的反应。氯N-（N，N-二乙基硫代氨基甲酰基）-苯甲酰胺基]双（二甲基苯基膦）氮化or（V），[ReN（Cl）（Me2PhP）2（Et2tcb）]和{bis（μ-乙基二硫代磷酸根-S）的X射线晶体结构，S'，O）二[双（二甲基苯基膦）氮化or（V）]}，[ReN（Me2PhP）2Etdtp）] 2

  摘要：

  摘要从[ReNCl 2（Me 2 PhP）3]合成了Novel与叔膦和二齿螯合配体的新型混合配体配合物。与二乙基二硫代氨基甲酸酯（Et 2 dtc-），N-（N，N-二烷基硫代氨基甲酰基）苯甲酰胺酸酯（R 2 tcb-）和二苯基二硫代次膦酸酯（S 2 PPh 2-）通式[ReN（Cl）（Me 2 PhP）2 L]形成。与O，O'-二乙基二硫代磷酸酯（Et 2 dtp-）的类似反应产生二聚化合物[ReN（Me 2 PhP）2（Etdtp）] 2，其中二硫代磷酸酯的每个乙基均被除去，所得的Etdtp 2-充当三齿桥接配体。[ReN（Cl）（Me 2 PhP）2（Et 2 tcb）]在空间群P 1中结晶三斜晶。其中a = 9.774（3），b = 11.993（3），c = 13.707（4）A，α= 92.29（2），β= 91.00（2）和γ= 98.03（6°，Z = 2。 R值为0。基于

  DOI：

  10.1016/s0020-1693(00)82829-7

文献信息

• Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone
  作者：D. V. Griffiths、S. J. Parrott、M. Togrou、J. R. Dilworth、Yifan Zheng、S. Ritter、U. Abram

  DOI：10.1002/(sici)1521-3749(199809)624:9<1409::aid-zaac1409>3.0.co;2-k

  日期：1998.9

  Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl2(PPh3)(2)] and [ReN(PMe2Ph).(S2CNEt)(2)], respectively. [ReNCl2(PPh3)(2)] reacts with 1.5 equivalents of KS2CNEt2 in methanol to yield the unusual dark red species [cyclo-ReN}(4)(S2CNEt2)(6)(MeOH)(2).(PPh3)(2)][BPh4](2). CH2Cl2. 2H(2)O (1). The crystal structure of the tetramer (triclinic, space group P (1) over bar, a = 13.842(2), b = 15.213(2), c = 16.796(3) Angstrom, alpha = 67.88(1), beta = 70.90(1), gamma = 88.05(1)degrees, U = 3080.2(8) Angstrom(3), Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re=N-Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the cyclo-ReN}(4) core is obtained from the reaction of [ReN(PMe2Ph)(S2CNEt2)(2)] with Al2Cl6 in acetone. [cyclo-ReN}(4)(S2CNEt2)(4)Cl-4.(PMe2Ph)(4)]. 2 acetone (2) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Angstrom, beta = 102.37(1)degrees, U = 8048(4) Angstrom(3), Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered ReN}(4) ring contains asymmetric Re=N-Re bridges (mean values: 1.69 Angstrom and 2.029 Angstrom, respectively). In contrast, reaction of [ReNCl(S2CNEt2)(PMe2Ph)(2)] with one equivalent of K[S2CN(Me)CH2CH2NMe3]I gave the mixed dithiocarbamato-cation [ReN(S2CNEt2).(S2CN(Me)CH2CH2NMe3)(PMe2Ph)](+) (3) which was isolated as a tetraphenylborate salt.