^TMSCp₂Ti(C₂Fc)₂ | 196926-05-3

• 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: ^TMSCp₂Ti(C₂Fc)₂
• 英文别名: (η(5)-C5H4SiMe3)2Ti(CC(η(5)-C5H4)Fe(η(5)-C5H5))；(η(5)-C5H4SiMe3)2Ti(C.tplbond.C(ferrocenyl))2；(η5-C5H4SiMe3)2Ti(CCFc)2；(η(5)-C5H4SiMe3)2Ti(-C*C-(η(5)-C5H4)Fe(η(5)-C5H5))2；(η5-C5H4SiMe3)2Ti(C.tplbond.C(η5-C5H4)Fe(η5-C5H5))2；(eta.5-C5H4SiMe3)2Ti(bis(ferrocenylethynyl))；cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(trimethyl)silane;5-ethynylcyclopenta-1,3-diene;iron(2+);titanium(4+)
• CAS: 196926-05-3
• 化学式: C₄₀H₄₄Fe₂Si₂Ti
• 分子量: 740.534
• InChiKey: WBPFYOFKRSWKJK-UHFFFAOYSA-N

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：

  ^TMSCp₂Ti(C₂Fc)₂ 在 AgPF₆ 作用下， 以 丙酮 为溶剂， 生成 1,4-bis(ferrocenyl)-1,3-butadiyne
  参考文献：
  名称：

  C₂-Bridged Titanocene−Ferrocenyl Complexes:  Synthesis, Reaction Chemistry, and Electrochemical Behavior

  摘要：

  LiC=CFc (2; Fc = (eta(5)-C5H4)(eta(5)-C5H5)Fe) reacts with [Ti]Cl-2 (1a) ([Ti] = (eta(5)-C5H4SiMe3)(2)-Ti) in a 2:1 molar ratio to produce the C-2-bridged titanocene-ferrocenyl complex [Ti](C=CFc)(2) (3). While treatment of heterotrinuclear 3 with Ni(CO)(4) (4) affords the heterotetranuclear tweezer complex {[Ti](C=CFc)(2)}Ni(CO) (5), reaction of 3 with NiCl2 (6) yields Fc-C=CC=C-Fc (7) along with [Ti]Cl-2 (1a) and Ni-0 in a redox reaction. 7 can also be synthesized in the chemical oxidation of 3 with 2 equiv of AgPF6. The electrochemical behavior of compounds 3 and 5 is discussed. The X-ray structure analysis of complex 3 is reported.

  DOI：

  10.1021/om9701231
• 作为产物：
  描述：

  bis(η5-trimethylsilylcyclopentadienyl)titanium(IV)dichloride 、 lithium ferrocenylacetylide 以 四氢呋喃 为溶剂， 生成 ^TMSCp₂Ti(C₂Fc)₂
  参考文献：
  名称：

  Reductive coupling reaction induced by remote-site oxidation in titanocene bis(metallocenylacetylide), where metallocenyl = ferrocenyl or ruthenocenyl: a novel route to Cn (n = 4, 6, and 8) wire with the metallocenyl groups at both terminals

  摘要：

  The titanocene bis(acetylide) complexes (eta(5)-C5H4R)(2)Ti[(C=C)(m)-Mc][(C=C)(n)-Mc'] (R = H, SiMe3; m, n = 1 or 2; Mc, Mc' = ferrocenyl or ruthenocenyl) have been prepared and found to be easily oxidized with 2 equiv. amount of AgPF6 liberating a neutral product, Mc-(C=C)(m)(C=C)(n)-Mc'. Electrochemical studies indicate that the reaction is induced by initial oxidation of Mc and Mc' followed by unprecedented reductive coupling of the two alkynyl carbons bound to titanocene. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(97)00149-6

文献信息

• Synthesis, electrochemistry and electronic spectra of tetranuclear bis(η2-alkynyl) transition-metal complexes. The molecular structure of [(η5-C5H4SiMe3)2Ti(CCFc)2]CuBr
  作者：Stephan Back、Gerd Rheinwald、Heinrich Lang

  DOI：10.1016/s0022-328x(00)00040-1

  日期：2000.4

  Br ligand. The Fc groups are both positioned on one side of the Ti(CC)2Cu plane, while the Br ligand points towards the opposite side and is located 0.2566(57) Å out of this array. The electronic spectra of complexes 2b (M=Cu) and 3a (M=Ag) show a bathochromic shift of λmax upon η2-coordination of the FcCC units in 1 to the M(I) centre in 2b or 3a. Cyclic voltammetric studies reveal a behaviour dependent

  [Ti]（CCFc）2 } MX型四金属配合物（M = Cu：2a， X = Cl; 2b，X = Br; 2c：X = OTf; M = Ag：3a，X = Cl; 3b，X = BF 4 ;钛[Ti] =（η 5 -C 5 H ^ 4森达3）2的Ti，FC =（η 5 -C 5 H ^ 4）的Fe（η 5 -C 5 H ^ 5），光学传递函数= OSO 2 CF 3）通过三核的反应钛[Ti]（CCFc）中合成2（1）和一当量的[MX]（M = Cu，Ag; X = Cl，Br，OTf，BF 4）。钛[Ti]（CCFc）的固态结构2 }的CuBr（图2b）显示三维坐标的两个η的Cu（I）中心2个配位的CCFc单元和η 1结合的配体溴。Fc基团均位于Ti（CC）2 Cu平面的一侧，而Br配体指向相反的一侧，并位于该阵列之外的0.2566（57）Å。复合物的电子光谱2b中（M =
• First Example of Zinc(II) Monomeric Species Stabilized by η²-Bonded Alkynes
  作者：Heinrich Lang、Noelia Mansilla、Gerd Rheinwald

  DOI：10.1021/om000914u

  日期：2001.4.1

  Monomeric ZnX2 (X = Cl, Br) moieties have been stabilized by alkynes through the reaction of [Ti](C⋮CR)2 (R = SiMe3 (1), Fc (2); Fc = (η5-C5H4)Fe(η5-C5H5), [Ti] = (η5-C5H4SiMe3)2Ti) with the anhydrous Zn(II) salts ZnX2 (X = Cl (3), Br (4)). The resulting heterodinuclear complexes of formula [Ti](C⋮CR)2}ZnX2 (R = SiMe3, X = Cl (5a), Br (5b); R = Fc, X = Cl (6a), Br (6b)) could be obtained in high yield

  单体ZNX 2（X =氯，溴）部分已经通过钛[Ti]的反应而稳定由炔烃（C⋮CR）2（R =森达3（1），FC（2）; FC =（η 5 -C 5 ħ 4）的Fe（η 5 -C 5 H ^ 5），钛[Ti] =（η 5 -C 5 H ^ 4森达3）2 Ti）的与所述无水的Zn（II）盐ZNX 2（X =氯（3） ，Br（4））。所得的式[Ti]（C⋮CR）2 } ZnX 2异核复合物（R ＝ SiMe 3，X ＝ Cl（5a），Br（5b）； R ＝ Fc，X ＝ Cl（6a），Br（6b））可以高收率获得。所有新配合物的身份已通过分析和光谱（IR，1 H和13 C 1 H} NMR）数据确认。另外，已经通过X射线衍射建立了配合物6b的结构。在分子内已经遇到了两个不同的方向（6b 1和6b 2）。的固态结构6b中清楚地表明了η 2的FCC⋮的C协调配体ZnBr如图2所示，导致锌（II
• Zur Umsetzung von Bis(alkinyl)-Titanocenen mit Übergangsmetall-Verbindungen von Cu(II), Pd(II), Pt(II), Fe(III) und Au(III)
  作者：W. Frosch、S. Back、K. Köhler、H. Lang

  DOI：10.1016/s0022-328x(00)00067-x

  日期：2000.4

  MX2 (M=Pd, Pt; X=Cl; M=Cu; X=Cl, Br, OAc, acac) and MCl3 (M=Fe, Au) is described. All reactions are dominated by redox processes. Generally, the reaction of 1 or 5a–5c with AuCl3 or MCl2 (M=Cu, Pd, Pt) produces the titanocene dichloride [Ti]Cl2 (3a) along with the corresponding butadiynes R1CCCCR2 (4: R1=R2=Fc; 7a: R1=R2=SiMe3; 7b: R1=R2=C6H5; 7c: R1=SiMe3, R2=C6H5) and M(0) (M=Cu, Au, Pd, Pt). As

  双（炔基）二茂钛的反应行为钛[Ti]（CCR 1）（CCR 2）[钛] =（η 5 -C 5 H ^ 4森达3）2的Ti; 1，R 1 = R 2 = FC，FC =（η 5 -C 5 H ^ 4）的Fe（η 5 -C 5 H ^ 5）; 5a：R 1＝ R 2＝ SiMe 3；5b：R 1＝ R 2＝ C 6 H 5；5c：R 1 = SiMe 3，R 2 = C 6 H 5 }，朝向MX 2（M = Pd，Pt; X = Cl; M = Cu; X = Cl，Br，OAc，acac）和MCl 3（M = Fe ，Au）被描述。所有反应均由氧化还原过程控制。通常，反应1或图5a - 5c中与AUCL 3或的MC1 2（M =铜，钯，铂）产生二氯二茂钛钛[Ti]氯2（图3a）与相应的沿butadiynesř 1个CCC CR 2（4：R 1 = R 2 = Fc;7a：R 1＝
• Titanocene-based group-11 metal ions; solid-state structure of {[(η5-C5H4SiMe3)2Ti(CCPh)2]2Ag}NO3
  作者：H. Lang、T. Stein、S. Back、G. Rheinwald

  DOI：10.1016/j.jorganchem.2004.04.048

  日期：2004.8

  X = FBF3; M = Ag: 4b, X = OClO3; 4c, X = ONO2) is reacted with one equivalent of 1b. Transferring this reaction scheme to [Ti](CCSiMe3)2 (1c) only the formation of the heterobimetallic tweezer complex [Ti](μ-σ,π-CCSiMe3)2}MX 4d, MX = [Cu(NCCH3)]BF4; 4e, MX = AgOClO3} is observed which is attributed to the bulkiness of the acetylide-bound Me3Si group. The solid-state structure of 3e is reported. In 3e, two

  钛[Ti]（CCR）的反应2 钛[Ti] =（η 5 -C 5 H ^ 4森达3）2的Ti; 图1A，R = FC，FC =（η 5 -C 5 H ^ 4）的Fe（η 5 -C 5 H ^ 5）; 1b，R ＝ Ph}，其中MX 2a，MX ＝ [Cu（NCCH 3）4 ] BF 4；M = Ag; 2b，X ＝ ClO 4；X ＝ ClO 4。2c，X = NO 3 }以2：1的摩尔比产生三核异双金属（Ti 2M）或七核杂三金属（Ti 2 MFe 4）配合物[[Ti]（μ-σ，π-CCR）2 } 2 M] X（R = Fc：3a，M = Cu，X = BF 4 ; 3b， M =银，X = CLO 4 R = Ph值：3C，M =铜，X = BF 4 ; 3D，M =银，X = CLO 4：3E，M =银，X = NO 3）以高收率。当[Ti]（μ-σ，π-CCPh）2 } MX（M
• The reaction of titanocene bis(ferrocenylacetylide) and bis(ruthenocenylacetylide) with silver cation: formation of bis(Ti-tweezers) silver complexes
  作者：Yukiko Hayashi、Masahisa Osawa、Kimiko Kobayashi、Takuma Sato、Masaru Sato、Yasuo Wakatsuki

  DOI：10.1016/s0022-328x(98)00785-2

  日期：1998.10

  Titanocene bis(acetylide) where the acetylide has ferrocenyl or ruthenocenyl terminal group (C5H4R)(2)Ti(C=C)(n)-Mc}(2), reacted with 0.5 equivalent amount of AgPF6 giving cationic heptanuclear complexes of the form [(C5H4R)(4)Ti-2(C=C)(n)-Mc}(4)Ag](PF6) (la: R = SiMe3, n = 1, Me = ferrocenyl, 2a: R = H, n = 2, Me = ferrocenyl, 3a: R = SiMe3, n = 2, Me = ferrocenyl, 4a: R = SiMe3, n = 1, Me = ruthenocenyl) in good yields. Likewise, complex [(C5H4SiMe3)(4)Ti-2(C=CPh)(4)Ag](PF6) (5a) was isolated. The Ti(IV)-Fe(II)-Ag(I) complex 3a was structurally characterized to confirm the solid-state geometry of the first bis(Ti-tweezers) type chelate complex with silver cation in which the silver was coordinated by four triple bonds of the two titanocene bis(acetylide) moieties. The similar Ti(IV)-Ru(IH)-Ag(I) complex 4a was also characterized by single-crystal X-ray analysis. Complex 3a reacted with 1.5 equivalents (with respect to Ti) of AgPF6 to liberate Fc-(C=C)(4)-Fe (Fc = ferrocenyl) quantitatively. (C) 1998 Elsevier Science S.A. All rights reserved.