bis(pentamethylcyclopentadienyl)titanium(III) tert-butoxide | 107495-38-5

• 英文名称: bis(pentamethylcyclopentadienyl)titanium(III) tert-butoxide
• 英文别名: (η5-C5Me5)2TiO(t)Bu；[(η5-C5Me5)2Ti(III)O(t)Bu]；Cp*2TiOtBu；(η5-pentamethylcyclopentadienyl)2TiOtBu
• CAS: 107495-38-5
• 化学式: C₂₄H₃₉OTi
• 分子量: 391.453
• InChiKey: XRTLPDZIGQNHLH-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  bis(tricarbonyl(η-cyclopentadienyl)tungsten) 、 bis(pentamethylcyclopentadienyl)titanium(III) tert-butoxide 以 甲苯 为溶剂， 以61%的产率得到Cp*2Ti(O(t)Bu)(μ-CO)W(CO)2Cp
  参考文献：
  名称：

  钛氧烷（III）诱导的金属羰基二聚体的金属键断裂，钛醇盐在异双金属配合物中的作用,钛氧烷（III）诱导的金属羰基二聚体的金属键断裂，钛醇盐在异双金属配合物中的作用

  摘要：

  一系列钛茂（III）醇盐L 2 Ti（III）OR其中L = Cp，R = Et（1b），t Bu（1a），2,6-Me 2 C 6 H 3（1c），2,6 -吨卜2 -4-ME-C 6 H ^ 2（1D），或L =的Cp *，R =我（2E），吨BU（图2a）中，Ph（2F）合成，并进行与[CPM反应（ CO）3 ] 2 [M = Mo，W]，[CpRu（CO）2 ] 2和Co 2（CO）8。Ti（III）前体1a，1c，2a，2e和2f与[CpM（CO）3 ] 2 [M = Mo，W]反应形成异双金属配合物L 2 Ti（OR）（μ-OC）（CO ）2 MCp [M = Mo，W]，其中Ti和M通过异羰基桥连接。用Co这些钛（III）络合物的反应2（CO）8导致形成的Ti-Co的1双核配合物，Cp2为非*的Ti（OtBu）（μ-OC）的Co（CO）3从图2a，2e中，或2F，或Ti–Co

  DOI：

  10.1016/j.jorganchem.2004.09.075
• 作为产物：
  描述：

  (pentamethylcyclopentadienyl)(π-η(5):σ-η(1)-tetramethylfulvene)titanium(III) 、 叔丁醇 以 正己烷 为溶剂， 以82%的产率得到bis(pentamethylcyclopentadienyl)titanium(III) tert-butoxide
  参考文献：
  名称：

  Evaluation of the Oxygen π-Donation in Permethyltitanocene Silanolates and Alcoholates

  摘要：

  A series of compounds [Cp*Ti-2(III)OR'] where R' is (Pr3Si)-Pr-i (2), Ph3Si (3), ((BuO)-Bu-t)(3)Si (4), (c-C5H9)(7)Si8O12 (5), and Bu-t (6) were prepared by protolysis of the titanium-methylene bond in singly tucked-in permethyltitanocene [Cp*Ti(III)(eta(5):eta(1)-C5Me4CH2)] with the respective silanols or tert-butanol. Their electronic transitions from the ground-state molecules to their first excited states (dominantly a 1a(1) -> b(2) transition) occur in the range 1300-1800 nm, originating from pi-donation from oxygen lone pair electrons to the Ti-O bond (as found by Andersen et al. J. Am. Chem. Soc. 1996, 118, 1719). The X-ray crystal structures of 2-4 and 6 revealed that steric effects of substituents R' change the geometry of the titanocene moiety only negligibly. DFT calculations of the 1a(1) -> b(2) transition for optimized structures of 2, 4, 6, [Cp*Ti-2(III)OH] (7), and [Cp*Ti-2(III)OMe] (8) reproduced the dependence of experimental lambda(1a(1) -> b(2)) on electron donation/attraction properties of R' and revealed that the decrease of the oxygen T-donation is accompanied with an increase in negative natural charge on the OR' group. The observed increase of lambda(exp)(1a(1) -> b(2)) in the order of substituents R', Me < Bu-t < H < Ph < (SiPr3)-Pr-i < SiPh3 similar to Si((OBu)-Bu-t)(3) < (c-C5H9)(7)Si8O12 (SIPOSS cluster), thus indicates the decrease of Ti-O pi-interaction with an increased polarity of the Ti-O bond. The DFT calculations of 7 with the naturally bent and collinear Ti-O-H conformation showed only a small effect of bending on the oxygen pi-donation.

  DOI：

  10.1021/om801209f

文献信息

• Novel Titanium−Cobalt Complexes Formed by Reductive Cleavage of a Co−Co Bond in Co₂(CO)₈ by Titanocene <i>tert</i>-Butoxides:  Synthesis, Characterization, and Mechanistic Aspects for Metal−Metal Bond Recombination
  作者：Shota Niibayashi、Kaoru Mitsui、Kouki Matsubara、Hideo Nagashima

  DOI：10.1021/om0340701

  日期：2003.11.1

  Reactions of titanium(III) complexes (η5-C5R5)2TiOtBu (R = H (1), Me (4)) with Co2(CO)8 are found to be efficient methods to synthesize Ti−Co heterobimetallic complexes. A Ti−Co3 complex, (η5-C5H5)2Ti(OtBu)(μ4-OC)Co(CO)9 (3), was formed from 1 and Co2(CO)8, whereas a Ti−Co bimetallic complex, (η5-C5Me5)2Ti(OtBu)(μ-OC)Co(CO)3 (5), was obtained by the reaction of 4 with Co2(CO)8. In both cases, the reaction

  钛的反应（III）络合物（η 5 -C 5 - [R 5）2的TiO吨卜（R = H（1）中，Me（4））用Co 2（CO）8被发现是有效的方法来合成性Ti- Co异双金属配合物。甲的Ti-Co 3络合物，（η 5 -C 5 H ^ 5）2的Ti（O吨卜）（μ 4 -OC）的Co（CO）9（3）中，从形成1和Co 2（CO）8，而Ti-Co双金属配合物（η通过4与Co 2（CO）8的反应获得5 -C 5 Me 5）2 Ti（O t Bu）（μ-OC）Co（CO）3（5）。在两种情况下，反应均在5分钟内完成。通过NMR，IR和X射线晶体学对产物进行完全表征。配合物3包含四重桥连的CO基团，其氧末端连接至Ti部分，而碳末端结合至Co 3（CO）9部分中的三个Co原子。相反，络合物5是双核的，其Ti原子与Co（CO）连接3个基团由异羰基桥连而成。甲η 5 -C 5 H ^ 5类似物5，[（η 5
• Monomeric bis(pentamethylcyclopentadienyl)titanium(III) complexes with halide, borohydride, amide, alkoxide, and carboxylate ligands. X-ray structure of bis(pentamethylcyclopentadienyl)titanium(III) chloride
  作者：Johannes W. Pattiasina、Hero J. Heeres、Fre Van Bolhuis、Auke Meetsma、Jan H. Teuben、Anthony L. Spek

  DOI：10.1021/om00148a019

  日期：1987.5