cis-[Ni(Ph2PCHC(O)CH3)2] | 133752-02-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-[Ni(Ph2PCHC(O)CH3)2]
• CAS: 133752-02-0
• 化学式: C₃₀H₂₈NiO₂P₂
• 分子量: 541.189
• InChiKey: DFUWELLDJVGUGJ-YIRPGODZSA-L

反应信息

• 作为反应物：
  描述：

  cis-[Ni(Ph2PCHC(O)CH3)2] 、 cobalt(II) iodide 以 乙醚 为溶剂， 以43%的产率得到cis-[Ni(Ph2PCHC(O)Me)2]CoI2 * 0.25 C7H8
  参考文献：
  名称：

  Reactivity of α-Phosphino Enolate Complexes of Nickel(II) and Palladium(II) toward Electrophilic Metal Centers. Synthesis and Crystal Structures of the Bimetallic Palladium(II)−Gold(I) Complex [(dmba)Pd{Ph₂PCH(AuPPh₃)C(O)Ph}](BF₄) and of the Nickel(II)−Cobalt(II) Paramagnetic Complex cis-[Ni{Ph₂PCH C( O)(p-C₆H₄CH₃}₂]CoI₂

  摘要：

  The chemoselective reactivity of metal-coordinated phosphino enolates has been studied by the reactions of cis-[Ni{R'(2)PCHsic)C((sic)O)R}(2)] (R = Ph, p-C(6)H(4)Me, Me; R' = Ph, Pr-i, not all combinations) and [(C N)Pd{Ph(2)PCH(sic)C((sic)O)Ph}] (C N = o-C(6)H(4)CH(2)NMe(2), dmba or C10H8N, 8-mq) with different metal electrophiles. In the reaction of cis-[Ni{Ph(2)PCH(sic)C((sic)O)Ph}(2)] (1a) with [PtCl2(COD)] (COD = 1,5-cyclooctadiene), a transmetalation of the P,O ligands was observed, yielding the known complex cis-[Pt{Ph(2)PCH(sic)C((sic)O)Ph}(2)] (3). However, reaction of cis-[Ni(R'2PCH(sic)C((sic)O)R}(2)] with anhydrous CoI2 afforded the heterobinuclear complexes cis-[Ni{R'2PCH(sic)C((sic)O)R}(2)]CoI2 (5a, R = Ph, R' = Ph; 5b, R = p-C(6)H(4)Me, R' = Ph; 5c, R = Me, R' = Ph; 7, R = Ph, R' = Pr-i) which contain the phosphino enolate ligand in an unusual chelating-bridging mu-eta(1)(O):eta(2)(P,O) coordination mode in a nonplanar NiO2Co unit. The magnetic properties of these complexes are discussed. The SHOP-type catalyst [Ni(Ph){Ph(2)PCH(sic)C((sic)O)Ph}(PPh(3))] also behaved as an oxygen-donor metalloligand toward CoI2 to give a paramagnetic Co(II) complex. In contrast, reaction of [(C N)Pd{Ph(2)PCH(sic)C((sic)O)Ph}] with [Au(PPh(3))](+) occurred with formation of [(dmba) Pd{Ph(2)PCH(AuPPh(3))C(O)Ph}](BF4) (4a) in which a C-enolate-Au bond has been formed while the P,O chelate has remained coordinated to palladium. This reaction generates a new stereogenic center, as also evidenced by H-1 NMR spectroscopy. The solid state structures of complexes 4a . 1/2C(7)H(8) and 5b . CH2Cl2 have been determined by single-crystal X-ray diffraction: 4a . 1/2C(7)H(8) crystallizes in the triclinic space group P (1) over bar with Z = 2 in a unit cell of dimensions a = 16.778(4) Angstrom, b = 14.269(5) Angstrom, c = 10.838(6) Angstrom, alpha = 79.27(4)degrees, beta = 71.59(3)degrees, and gamma = 72.68(2)degrees; 5 . CH2Cl2 crystallizes in the monoclinic space group P2(1)/n with Z = 4 in a unit cell of dimensions a = 12.940(1) Angstrom, b = 18.329(2) Angstrom, c = 18.495(2) Angstrom, and beta = 91.627(8)degrees. The structures have been solved from diffractometer data by direct and Fourier methods and refined by full-matrix least-squares methods on the basis of 7240 (4a . 1/2C(7)H(8)) and 3644 (5b . CH2Cl2) observed reflections to R and R(w) values of 0.0363 and 0.0406 (4a . 1/2C(7)H(8)) and 0.040 and 0.038 (5b . CH2Cl2), respectively.

  DOI：

  10.1021/ic9513494