| 545357-41-3

• CAS: 545357-41-3
• 化学式: C₂₈H₂₂Cl₄N₄OPRe
• 分子量: 789.502
• InChiKey: JBBRXZKUPHHHDI-TWPNBRPISA-K

反应信息

• 作为产物：
  描述：

  、 三苯基膦 以 二氯甲烷 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Chemistry of azopyrimidine chelates of ReVO, ReIIIOPPh3 and ReVNAr

  摘要：

  The concerned azo ligands are L-1, L-2 and L-3 (general abbreviation L) in which the aryl groups are phenyl, p-chlorophenyl and o,p-dichlorophenyl, respectively. The reaction of L-1 with KReO4 in hot concentrated HCl affording [(ReOCl3)-O-V(L-2)] (2a), is attended with aryl chlorination. A similar reaction with L-2 furnished [(ReOCl3)-O-V(L-3)] (2b). The oxo complexes spontaneously reacted with PPh3 and ArNH2 furnishing [Re-III(OPPh3)Cl-3(L)] (3) and [Re-V(NAr)Cl-3(L)] (4), respectively. Unlike 2 and 4, 3 displays large paramagnetic H-1 NMR shifts. The type 2 species exhibit an irreversible electrochemical Re-V --> Re-VI oxidation near 2.2 V versus SCE. In type 4 species the Re-VI/Re-V couple occurs near 1.5 V and in type 3 species the. Re-IV/Re-III couple lies near 1.2 V. Structure determination of 2b, [Re-III(OPPh3)Cl-3(L-1)] (3a) and [Re-V(NC6H4Cl-p)Cl-3(L-2)] (4b) have revealed uniform meridional geometry. In 2b the Re-O and in 4b the Re-N (imide) distances are 1.666(10) and 1.719(6) Angstrom, respectively, consistent with triple bonding. The Re-N bonds lying trans to the oxo oxygen 2b and to the imide nitrogen in 4b are substantially lengthened. The Re-N(azo) lengths are 2.072(13), 1.957(9) and 2.003(6) Angstrom in 2b, 3a and 4b, the corresponding N-N distances being 1.25(2), 1.318(11) and 1.305(9) Angstrom, respectively. In 3a dpi(Re)-pi* (azo) back-bonding is clearly present and in 4b electron flow to the azo (pi*) orbital occurs via the route ArN --> Re-V --> azo(pi*). The corresponding route in 2b is less effective because the oxo group is a poorer donor compared with the imido group. In the lattice of 4b noncovalent Cl...Cl and aromatic pi-stacking are present. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00023-8