Trimethyl-[selanyl-bis(trimethylsilyl)silyl]silane | 148808-60-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Trimethyl-[selanyl-bis(trimethylsilyl)silyl]silane
• 英文别名: trimethyl-[selanyl-bis(trimethylsilyl)silyl]silane
• CAS: 148808-60-0
• 化学式: C₉H₂₈SeSi₄
• 分子量: 327.623
• InChiKey: CMAHUKIUMHOEBM-UHFFFAOYSA-N

物化性质

• 沸点：
  258.2±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.08
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Trimethyl-[selanyl-bis(trimethylsilyl)silyl]silane 以 further solvent(s) 为溶剂， 生成 (In[SeSi(SiMe3)3]3)2(μ-1,2-bis(dimethylphosphino)ethane)
  参考文献：
  名称：

  Synthesis and Characterization of Group 13 and 15 Selenolates and Tellurolates and the x-ray Crystal Structures of Ga[TeSi(SiMe3)3]3, In[SeC(SiMe3)3]3, {In[SeSi(SiMe3)3]3}2(.mu.-DMPE), and P[SeSi(SiMe3)3]3

  摘要：

  A broad range of chalcogenolate complexes of group 13 and 15 elements have been isolated and studied. Metathesis of AlEt(2)Cl with (THF)LiSeSi(SiMe(3))(3) gave (THF)AlEt(2)[SeSi(SiMe(3))(3)] in good yield. Chalcogenolysis of Al[N(SiMe(3))(2)](3) With 3 equiv of HESi(SiMe(3))(3) (E = Se, Te) afforded Al[ESi(SiMe(3))(3)](3) (E = Se, Te). Treatment of GaCl3 with 3 equiv of (THF)(2)LiTeSi(SiMe(3))3 produced the homoleptic species Ga[TeSi(SiMe(3))(3)](3); likewise, addition of 3 equiv of (DME)LiSeC(SiMe(3))(3) to InCl3 yielded In[SeC(SiMe(3))(3)](3). Reaction of InCl3 with 3 equiv of (THF)(2)-LiSeSi(SiMe(3))(3) produced (THF)In[SeSi(SiMe(3))(3)](3) in low yield. Homoleptic chalcogenolates, In[ESi(SiMe(3))(3)](3) (E = Se, Te) were prepared by chalcogenolysis of InCp(3) (Cp = eta(5)-C5H5). Addition of THF, pyridine, or TMEDA (N,N,N',N'-tetramethylethylenediamine) to In[SeSi(SiMe(3))(3)](3) gave 1:1 adducts, (L)In[SeSi(SiMe(3))(3)](3) (L = THF, pyridine, TMEDA). Addition of DMPE (1,2-bis(dimethylphosphino)ethane) to In[SeSi(SiMe(3))(3)](3), produced a 1:1 complex In[SeSi(SiMe(3))(3)](3)(DMPE) that was characterized in solution by NMR spectroscopy; attempts to isolate the complex yielded instead the crystalline 2:1 adduct {In [SeSi(SiMe(3))(3)](3)}(2)(u-DMPE), whose X-ray structure was determined. Indium(I) complexes InESi(SiMe(3))3 (E = Se, Te) were isolated from either the metathesis of InCl with (THF)(2)LiESi(SiMe(3))3 or chalcogenolysis with InCp. Likewise, chalcogenolysis with TlCp produced TlESi(SiMe(3))3 (E = Se, Te). Reaction of PCl3 with (THF)(2)LiSeSi(SiMe(3))(3) produced P[SeSi(SiMe(3))(3)](3) in good yield. The arsenic derivative As[SeSi(SiMe(3))(3)](3) was isolated from the reaction of As(NMe(2))3 and 3 equiv of selenol. Similarly, the antimony and bismuth complexes M[ESi(SiMe(3))(3)](3) (M = Sbt E = Se, Te; M = Bi, E = Se, Te) were prepared in good yields by chalcogenolysis with Sb(NMe(2))3 or Bi[N(SiMe(3))(2)](3). Crystallographic data are as follows. Ga[TeSi(SiMe(3))(3)](3): monoclinic, P2(1)/c, Z = 4, a = 24.235(4) Angstrom, b = 13.808(3) Angstrom, c = 18.689(4) Angstrom, beta = 106.424(16)degrees, R = 0.0926, R(W) = 0.0731. In[SeC(SiMe(3))(3)](3): triclinic, P $($) over bar$$ l, Z = 2, a = 13.772(4) Angstrom, b = 13.778(4) Angstrom, c = 16.026(4) Angstrom, alpha = 74.25(2)degrees, beta = 75.27(2)degrees, gamma = 62.12(2)degrees, R = 0.0424, R(W) = 0.0476. {In[SeSi(SiMe(3))(3)](3)}(2)(u-DMPE): triclinic, Pl $($) over bar$$, Z = 2, a = 13.655(3) Angstrom, b = 13.8323(20) Angstrom, c = 18.442(3) Angstrom, alpha = 97.874(13)degrees, beta = 104.066(16)degrees, gamma = 113.708(15)degrees, R = 0.0323, R(W) = 0.0332. P[SeSi(SiMe(3))(3)](3): monoclinic, P2(l)/c, Z = 6, a = 22.706(4) Angstrom, b = 13.959(5) Angstrom, c = 17.619(3) Angstrom, beta = 93.851(14)degrees, R = 0.0554, R(W) = 0.0463.

  DOI：

  10.1021/ic00123a021
• 作为产物：
  描述：

  在 三氟甲磺酸 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以69%的产率得到Trimethyl-[selanyl-bis(trimethylsilyl)silyl]silane
  参考文献：
  名称：

  Alkyl-, silyl-, and germyl-substituted thiolate, selenolate, and tellurolate derivatives and interconversion of silyl species by chalcogen metathesis

  摘要：

  The preparation of a series of chalcogenolate species (sol)nLiEY(SiMe3)3 (sol = THF, n = 1, 2; sol = DME, n = 1; E = S, Se, Te; Y = C, Si, Ge) by direct insertion of elemental E into Li-Y bonds of (THF)3LiC(SiMe3)3, (THF)3LiSi(SiMe3)3, or (THF)3LiGe(SiMe3)3 is reported. Two derivatives, (THF)2LiSeSi(SiMe3)3 and (THF)LiSSi(SiMe3)3, are more conveniently prepared by novel chalcogen metathesis reactions whereby tellurium is displaced from (THF)2LiTeSi(SiMe3)3 by either Se or S in THF at -55-degrees-C. Protonation of the chalcogenolate anions leads to the stable chalcogenols, HEY(SiMe3)3, which have been fully characterized. In methyl isobutyl ketone (MIBK), the pK(a) values of HTeC(SiMe3)3, HTeSi(SiMe3)3, HTeGe(SiMe3)3, HSeC(SiMe3)3, HSeSi(SiMe3)3, and HSSi(SiMe3)3 are determined to be 9.3, 7.3, 7.4, 10.8, 8.3, and 10.7, respectively. The X-ray structure of the mono-THF adduct (THF)LiTeSi(SiMe3)3, prepared from (THF)Li[N(SiMe3)2] and HTeSi(SiMe3)3, is also described; it crystallizes in the triclinic space group P1BAR with a = 9.083(4) angstrom, b = 11.181(4) angstrom, c = 12.053(8) angstrom, alpha = 93.16(4)degrees, beta = 104.68(5)degrees, gamma = 96.63-degrees, R = 0.0300, and R(w) = 0.0372.

  DOI：

  10.1021/ja00068a039

文献信息

• Synthesis, structure, and reactivity of homoleptic tin(II) and lead(II) chalcogenolates and conversion to metal chalcogenides. X-ray crystal structures of {Sn[TeSi(SiMe3)3]2}2 and (PMe3)Sn[TeSi(SiMe3)3]2
  作者：Allen L. Seligson、John Arnold

  DOI：10.1021/ja00071a034

  日期：1993.9

  tin(II) and lead(II) tellurolates, selenolates, and thiolates incorporating bulky ESi(SiMe 3 ) 3 ligands (E=Te, Se, S) are described. The derivatives M[ESi(SiMe 3 ) 3 ] 2 (M=Sn:1, E=Te; 3, E=Se; 5, E=S. M=Pb: 2, E=Te; 4, E=Se; 6, E=S) are prepared via protonolysis of M [N(SiMe 3 ) 2 ] 2 with HESi(SiMe 3 ) 3

  描述了掺入大量 ESi(SiMe 3 ) 3 配体（E=Te、Se、S）的均质锡 (II) 和铅 (II) 碲酸盐、硒酸盐和硫醇盐的制备和表征。导数 M[ESi(SiMe 3 ) 3 ] 2 (M=Sn:1, E=Te; 3, E=Se; 5, E=S. M=Pb: 2, E=Te; 4, E=Se ; 6, E=S) 通过 M [N(SiMe 3 ) 2 ] 2 与 HESi(SiMe 3 ) 3 的质子分解制备
• Gerlach, Christopher P.; Arnold, John, Inorganic Chemistry, 1998, vol. 37, p. 2393 - 2399
  作者：Gerlach, Christopher P.、Arnold, John

  DOI：——

  日期：——
• Trivalent Lanthanide Selenolates and Tellurolates Incorporating Sterically Hindered Ligands and Their Characterization by Multinuclear NMR Spectroscopy and X-ray Crystallography
  作者：Douglas R. Cary、Graham E. Ball、John Arnold

  DOI：10.1021/ja00117a018

  日期：1995.3

  Homoleptic trivalent selenolates of La and Y have been isolated from the reaction of Ln[N(SiMe(3))(2)](3) (Ln = La, Ce) with 3HSeSi(SiMe(3))(3) in hexanes. Variable-temperature NMR studies suggest that La[SeSi(SiMe(3))(3)](3) behaves as a three-coordinate monomer in toluene, whereas data for the Y analogue are consistent with the dimeric structure Y[SeSi(SiMe(3))(3)](2)[mu-SeSi(SiMe(3))3]}(2). EXSY experiments have been used to investigate ligand exchange in the Y compound. THF adducts Ln[SeSi(SiMe(3))(3)](3)(THF)(2) (Ln = La, Sm, Yb) have been isolated and fully characterized. Tellurolate species Ln[TeSi(SiMe(3))(3)](3) (Ln = La, Ce), prepared by the analogous reaction with 3HTeSi(SiMe(3))(3) in hydrocarbons, were characterized by NMR spectroscopy and by the isolation of derivatives. Addition of DMPE (DMPE = 1,2-bis(dimethylphosphino)ethane) to these reactions gave isolable adducts Ln[TeSi(SiMe(3))(3)](3)(DMPE)(2) (Ln = La, Ce, Y) which have been characterized by multinuclear and variable-temperature NMR spectroscopy. in addition, the X-ray crystal structure of La[TeSi(SiMe(3))(3)](3)(DMPE)(2) has been determined: it crystallizes at -40 degrees C from hexanes in the space group C2/c with a = 51.207(11) Angstrom, b = 15.725(3) Angstrom, c = 18.903(3) Angstrom, beta = 92.698(15)degrees, V = 15204(9) Angstrom(3), d(calcd) = 1.37 g cm(-3), and Z = 8. Exchange spectroscopy has also been used to investigate the process by which these molecules rearrange in solution, The homoleptic tellurolates are unstable in solution as monitored by NMR spectroscopy; preparative-scale reactions led to the isolation of a remarkable tellurolate/telluride cluster Ce5Te3[TeSi(SiMe(3))(3)](9), which has been structurally characterized by X-ray crystallography. Ce5Te3 [TeSi(SiMe(3))(3)](9) crystallizes at -40 degrees C from hexanes in the space group P6(3)/m with a = 20.456(5) Angstrom, b = 20.456(5) Angstrom, c = 28.063(9) Angstrom, gamma = 120 degrees, V = 10170(8) Angstrom(3), d(calcd) 1.46 g cm(-3), and Z = 2.
• Synthesis and Reactivity of Group 4 Homoleptic Selenolates and Tellurolates:  Lewis Base Induced Conversion to Terminal and Bridging Chalcogenides
  作者：Christopher P. Gerlach、Victor Christou、John Arnold

  DOI：10.1021/ic9600689

  日期：1996.1.1
• Cary, Douglas R.; Arnold, John, Inorganic Chemistry, 1994, vol. 33, # 9, p. 1791 - 1796
  作者：Cary, Douglas R.、Arnold, John

  DOI：——

  日期：——