tris((2,6-diisopropylphenyl)imido)methylrhenium(VII) | 124943-38-0

• 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: tris((2,6-diisopropylphenyl)imido)methylrhenium(VII)
• 英文别名: MeRe(N(2,6-diisopropylphenyl)3)3；[(2,6-di-i-Pr2C6H3N=)3ReMe]
• CAS: 124943-38-0
• 化学式: C₃₇H₅₄N₃Re
• 分子量: 727.063
• InChiKey: SBAOBXBUMTXJQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.47
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  37.08
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  tris((2,6-diisopropylphenyl)imido)methylrhenium(VII) 以 氯仿 为溶剂， 生成 bis{(μ-(2,6-diisopropylphenyl)imido)bis((2,6-diisopropylphenyl)imido)methylrhenium(VII)}
  参考文献：
  名称：

  Herrmann, Wolfgang A.; Weichselbaumer, Georg; Paciello, Rocco A., Organometallics, 1990, vol. 9, # 2, p. 489 - 496

  摘要：

  DOI：
• 作为产物：
  描述：

  在 CH₃I 作用下， 以 not given 为溶剂， 生成 tris((2,6-diisopropylphenyl)imido)methylrhenium(VII)
  参考文献：
  名称：

  Williams, Darryl S.; Anhaus, Jens T.; Schofield, Mark. H., Journal of the American Chemical Society, 1991, vol. 113, p. 5480 - 5481

  摘要：

  DOI：

文献信息

• Kinetic and Mechanistic Studies of Sulfur Transfer from Imidomethylrhenium Sulfides
  作者：Wei-Dong Wang、Ilia A. Guzei、James H. Espenson

  DOI：10.1021/ic0255196

  日期：2002.9.1

  with a 1:1 amount of a phosphine or an alkyl isocyanide to yield a dimeric rhenium(VI) species, [CH(3)Re(NAr)(2)](2)(mu-S) (2), which has been structurally characterized. The two rhenium atoms in 2 are within bonding distance, 280 pm, more than 90 pm shorter than in 1. With excess L, 1 reacts to give a monomeric rhenium(V) complex, CH(3)Re(NAr)(2)L(2) (3A, L = PZ(3), Z = alkyl, aryl; 3B, L = isocyanide)

  双（2,6-二异丙基苯基亚氨基）甲基r（VII）硫化二聚体[CH（3）Re（NAr）（2）]（2）（mu-S）（2）（1）与1：1反应量的膦或烷基异氰化物生成二聚rh（VI）物种[CH（3）Re（NAr）（2）]（2）（mu-S）（2），已在结构上进行了表征。2中的两个rh原子的键合距离为280 pm，比1中的短90 pm。过量的L时，1发生反应生成单体rh（V）络合物CH（3）Re（NAr）（2） L（2）（3A，L = PZ（3），Z =烷基，芳基； 3B，L =异氰酸酯）。关于[1]，3A的形成速率是一阶的，相对于单齿膦浓度，3A的形成速率是二阶的。然而，对于双齿膦，关于膦的顺序下降为1。加入另一种（不可氧化的）配位体，例如吡啶或其衍生物之一，加速3A的形成。在吡啶配体的存在下，相对于膦浓度，该反应是一级的，无论是单齿的还是双齿的。膦与2之间的反应比与1之间的反应慢，这将[CH（3）
• Hydrolysis, Hydrosulfidolysis, and Aminolysis of Imido(methyl)rhenium Complexes
  作者：Wei-Dong Wang、Ilia A. Guzei、James H. Espenson

  DOI：10.1021/ic0000956

  日期：2000.9.1

  CH3Re(NAr)3 (1b, Ar = 2,6-diisopropylphenyl) and H2O in CH3CN at 313 K. Both 1a and 1b react with H2S to produce the rhenium(VII) sulfide, (CH3Re(NR)2)2(mu-S)2 (4a, R = Ad; 4b, R = Ar), with second-order rate constants of 17 and 1.6 x 10(-4) L mol-1 s-1 in C6H6 and CH3CN, respectively. Complex 4b has been structurally characterized. The crystal data are as follows: space group C2/c, a = 30.4831 (19) A, b

  三（亚氨基）甲基r配合物CH3Re（NAd）3（1a，Ad = 1-金刚烷基）与H2O反应生成CH3Re（NAd）2O（2a）和AdNH2。生成的二（亚氨基）氧代物质可以进一步与另一分子 反应生成CH3Re（NAd）O2（3a）。这些反应的动力学已经通过1 H NMR和UV-vis光谱学进行了研究。1a与 在298 K下在C6H6中反应的二级速率常数为3.3 L mol-1 s-1，比获得的值1 x 10（-4）L mol-1 s-1大得多CH3Re（NAr）3（1b，Ar = 2,6-二异丙基苯基）与 在313 K的CH3CN中反应的过程.1a和1b都与H2S反应生成硫化rh（VII），（CH3Re（NR）2 ）2（mu-S）2（4a，R = Ad; 4b，R = Ar），在 和CH3CN中的二阶速率常数分别为17和1.6 x 10（-4）L mol-1 s-1分别。配
• Multiple Bonds between Main-Group Elements and Transition Metals. 166.¹ Oxo/Imido Complexes of Heptavalent Rhenium:  Structures, Reactivity, and Behavior in Solution
  作者：Wolfgang A. Herrmann、Hao Ding、Fritz E. Kühn、Wolfgang Scherer

  DOI：10.1021/om971062+

  日期：1998.6.1

  state, the dimeric compounds are bridged by oxygen ligands, forming Re2O2 units, while in solution, nitrogen bridging is also evident. Formal replacement of all three oxo groups in 1 by (2,6-diisopropylphenyl)imido ligands leads to a compound of formula CH3Re(NR)3 (4). Complex 4 is monomeric both in solution, regardless of the temperature, and in the solid state. Ligand exchange processes take place via

  混合酰亚胺/氧代铼（VII）配合物，甲基三（VII）（正式衍生物1）与通式CH的（2,6-二异丙基）亚氨基配体3 REO 3 - X（NR）X（X = 1，和2 ；分别是化合物2和3）。通过动态1 H和17 O NMR光谱研究了它们的结构和在溶液中的行为。固态时，化合物2和3如X射线晶体学所示，其显示二聚体结构。在溶液中，单体和二聚体形式平衡存在。在升高的温度下，单体占主导地位。在固态下，二聚化合物通过氧配体桥接，形成Re 2 O 2单元，而在溶液中，氮桥联也是明显的。正式替代在所有三个氧代基团的1由（2,6-二异丙基）亚氨基配体的引线式CH的化合物3的Re（NR）3（4）。复杂4在溶液中，无论温度如何，它都是单体，并且在固态。如果将有机or氧化物与有机（（VII）酰亚胺/氧代物种或有机hen（VII）酰亚胺混合，则配体交换过程将通过二聚中间体进行。甲基双（亚氨基）单氧or（VII）（3）
• Synthesis and Reactivity of Tris(imido)rhenium Complexes Containing Rhenium−Main Group Element Bonds. Silicon−Carbon Bond Activations of PhSiH₃ by Silyl Complexes
  作者：John Gavenonis、T. Don Tilley

  DOI：10.1021/ic030282e

  日期：2004.7.1

  The synthesis and reactivity of a series of complexes of the (DippN=)(3)Re (Dipp = 2,6-(i)Pr(2)C(6)H(3)) fragment are reported. The anionic, Re(V) complex (THF)(2)Li(micro,micro-NDipp)(2)Re(=NDipp) (1), prepared by the reaction of (DippN=)(3)ReCl with (THF)(3)LiSi(SiMe(3))(3) or (t)BuLi (2 equiv) in the presence of THF (4 equiv), served as an important starting material for the synthesis of rhenium-element-bonded

  报告（DippN =）（3）Re（Dipp = 2,6-（i）Pr（2）C（6）H（3））片段的一系列配合物的合成和反应性。通过（DippN =）（3）ReCl与（THF）反应制得的阴离子Re（V）络合物（THF）（2）Li（micro，micro-NDipp）（2）Re（= NDipp）（1） ）（3）LiSi（SiMe（3））（3）或（t）BuLi（2当量）在THF（4当量）存在下用作合成the元素键合配合物的重要原料。例如，用ClSiR（3）处理1得到相应的甲硅烷基络合物（DippN =）（3）ReSiR（3）（SiR（3）= SiMe（3）（2a），SiHPh（2）（2b），SiH （2）Ph（2c））。认为络合物2a-c在Re（VII）（DippN =）（3）ReSiR（3）和Re（V）（DippN =）（2）ReN（SiR（3））Dipp异构体之间平衡存在。配合物2a，b与Ph
• Synthesis and reactivity of a series of analogous rhenium tris(imido), bis(imido) alkyne, and imido bis(alkyne) complexes
  作者：Darryl S. Williams、Richard R. Schrock

  DOI：10.1021/om00028a032

  日期：1993.4

  A reaction between Re2O7, ArNH2 (Ar = 2,6-C6H3-i-Pr2), NEt3, and Me3SiCl yields Re(NAr)3Cl. Reduction of Re(NAr)3Cl in THF by 1 equiv of sodium amalgam gives Hg[Re(NAr)s]2 in ca. 50% yield. An X-ray study showed Hg[Re(NAr)3]2 to be composed of molecular units of (ArN)3Re-Hg-Re(NAr)3 having a linear Re-Hg-Re bond and nearly trigonal planar staggered Re(NAr)3 units. Reduction of either Hg[Re(NAr)3]2 or Re(NAr)3Cl by 2 equiv of sodium amalgam in THF affords Na(THF)2Re(NAr)3 in high yield. An X-ray structure of [N(PPh3)2][Re(NAr)3] showed that the [Re(NAr)3]- ion is a trigonal planar species in which the Re-N-C angles all are essentially linear. Compounds that contain the [Re(NAr)3]- ion can be alkylated to give compounds of the type Re(NAr)3R and protonated to give Re(NAr)3H. Reactions between Re(NAr)3H and pi-acceptor ligands yield pseudotetrahedral compounds of the type Re(NAr)2(NHAr)(eta2-L) [L = C2H2, C2Me2, OCHCMe3, C2H4, or norbornene]. Addition of 2 equiv of pyHCl to Re(NAr)3Cl yields Re(NAr)2Cl3(PY). Reduction of Re(NAr)2Cl3(PY) with sodium amalgam in THF in the presence of MeC=CMe or NpC=CNp (Np = neopentyl) yields complexes of the type Re(NAr)2(eta2-C2R2)Cl. Reduction of Re(NAr)2(eta2-C2NP2)Cl by 1 equiv of sodium amalgam yields Hg[Re(NAr)2(eta2-C2NP2)]2, while reduction by 2 equiv of sodium amalgam yields pentane-soluble Na(THF)2Re(NAr)2(eta2-C2Np2). Na(THF)2Re(NAr)2(eta2-C2Np2)reacts with MeI or ClCH2-2,4,6-C6H2Me3 to yield Re(NAr)2(eta2-C2NP2)R or with [Et2NH2][OTf] in THF to give Re(NAr)2(eta2-C2NP2)H. Addition of excess PMe2Ph to Re(NAr)2(eta2-C2NP2)H yields Re(NAr)2(PMe2Ph)2H. Addition of 4 equiv of pyridinium chloride in a 1:5 mixture of THF and pyridine to Na(THF)2Re(NAr)3 affords Re(NAr)Cl3(PY)2 in high yield. Re(NAr)Cl3(PY)2 is reduced by excess Zn dust in the presence of 2 equiv of dineopentylacetylene in refluxing THF to afford Re(NAr)(eta2-C2NP2)2Cl. Reduction of Re(NAr)(eta2-C2NP2)2Cl by 1 or 2 equiv of sodium amalgam in THF yields Hg[Re(NAr)(eta2-C2NP2)2]2 or Na(THF)2Re(NAr)(eta2-C2NP2)2, respectively. The molecular structure of Na(THF)2Re(NAr)(eta2-C2Np2)2 shows that [Na(THF)2]+ is bound to the imido nitrogen atom (2.464(9) angstrom), not to rhenium (Re-Na = 3.17 angstrom), and the coordination about the rhenium center is distorted from the pseudotrigonal planar geometry expected for [Re(NAr)(eta2-C2NP2)2]-. Na(THF)2Re(NAr)(eta2-C2NP2)2 is alkylated smoothly by MeI or ClCH2-2,4,6-C6H2Me3 to afford Re(NAr)(eta2-C2NP2)2R, while addition of [Et2NH2][OTf] yields pale yellow Re(NAr)(eta2-C2NP2)2H. Cyclic voltammograms (200 mV s-1) were obtained for the chloride derivatives and sodium salts of the tris-, bis-, and mono(imido) complexes in a solution of 0.5 M[NBu4][PF6] in THF. Extended Huckel calculations on [Re(NH)3]-, [Re(NH)2(C2H2)]-, and Re(NH)(C2H2)2]- all clearly show that a 20-electron count on the metal is avoided by filling a ligand-centered nonbonding orbital.