[(CptBu)2Ti(η2-bis(trimethylsilyl)acetylene)] | 848308-57-6

• 英文名称: [(CptBu)2Ti(η2-bis(trimethylsilyl)acetylene)]
• CAS: 848308-57-6
• 化学式: C₂₆H₄₄Si₂Ti
• 分子量: 460.686
• InChiKey: DYXHIJOVYDDPPE-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (E)-1,2-Di(pyridin-4-yl)diazene 、 正己烷 、 [(CptBu)2Ti(η2-bis(trimethylsilyl)acetylene)] 以 苯 为溶剂， 以51%的产率得到[((C5H4C(CH3)3)2Ti)4(cis-4,4'-azobispyridine)2]*hexane
  参考文献：
  名称：

  Reactions of Low-Valent Titanocene(II) Fragments with trans-4,4′-Azobispyridine (RN═NR, R = C₅H₄N): Formation of Tetranuclear Molecular Squares by trans−cis Isomerization

  摘要：

  The reactions of the low-valent titanocene sources [Cp*,-Ti(eta(2)-C-2(TMS)(2))] (2) and [tBuCp(2)Ti(eta(2)-C-2- (TMS)(2))] (3) with trans-4,4'-azobispyridine (8) leads to novel supramolecular squares [(Cp-2*Ti)(4)(mu(2)-N,N';eta(2)- -N,N'-C10H8N4)(2)] (10) and [(tBuCp(2)Ti)(4)(mu(2)-N,N';eta(2)-N,N'-C10H8N4)(2)] (11). These complexes consist of four bent-titanocene corner units and two azo ligands 8. Within this self-assembly process the azo ligands experience a conformational rearrangement from trans to cis. The titanocene moieties are embedded with two different N-donor environments, provided by the pyridyl rings and the azo functionality of 8. Single-crystal X-ray analyses of the tetranuclear compounds 10 and 11 revealed the structural features of these molecular polygons. Exclusively cis-configurated azopyridine units are detected in 10 and 11. Comparison of bond lengths and angles in coordinated and free ligands shows a reduced state of the bridging ligands in the low-valent titanium complexes 10 and 11. In such a way, the N-azo-N-azo distances are elongated from 1.251(2) angstrom in 8 to av 1.405(3) angstrom (10) and 1.434(3) angstrom (11), respectively. The syntheses and attributes of these novel compounds are discussed. From the reaction of [Cp2Ti(eta(2)-C-2(TMS)(2))] (1) with 8, 1,2-bis(4-pyridyl)hydrazine (13) was isolated and fully characterized as a subsequent product.

  DOI：

  10.1021/om801123k