cis-{-Ni(II)(-PH2P-CH-C-(O)-(cyclic)Ph)2} | 97954-27-3

• 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(II)(-PH2P-CH-C-(O)-(cyclic)Ph)2}
• 英文别名: cis-[Ni(Ph2PCHC(O)Ph)2]
• CAS: 97954-27-3
• 化学式: C₄₀H₃₂NiO₂P₂
• 分子量: 665.33
• InChiKey: LDVXGUKIIHPBJY-CYOKOSDRSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  45.0
• 可旋转键数：
  6.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  cis-{-Ni(II)(-PH2P-CH-C-(O)-(cyclic)Ph)2} 在 HCl 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷-D2 为溶剂， 生成 trans-dibromo-bis(diphenylphosphinomethyl phenylketone-P)nickel(II)
  参考文献：
  名称：

  Braunstein, Pierre; Matt, Dominique; Nobel, Dominique, Journal of the Chemical Society, Dalton Transactions, 1988, p. 353 - 362

  摘要：

  DOI：
• 作为产物：
  描述：

  trans-dichloro-bis(diphenylphosphinomethyl phenylketone-P)nickel(II) 在 NaOC₂H₅ 作用下， 以 乙醇 为溶剂， 以>99的产率得到cis-{-Ni(II)(-PH2P-CH-C-(O)-(cyclic)Ph)2}
  参考文献：
  名称：

  Phosphorus double functionalisation by template condensations; formation of P–C and P–O bonds from metallocycles. Synthesis and crystal structure of cis-[PdCl₂{Ph₂PCHC(Ph)OP(Ph)(o-C₆H₄CH₂NMe₂H}]Cl

  摘要：

  空气稳定的双螯合物顺式-[[图形省略])Ph}2](1)和[(L)[图形省略])Ph}][(3)，(LH)= 二甲基苄胺；(5)，(LH)= 8-甲基喹啉]与 1 等量的 PhPCl2 顺利反应，生成偶联产物[(2)、(4) 和 (6)]。的 PhPCl2 顺利反应，得到偶联产物[(2)、(4)和(6)]，其中涉及烯醇配体的 O 原子和环金属化配体的与 Pd 结合的 C 原子。

  DOI：

  10.1039/c39870001530

文献信息

• Bis-alkenyl complexes of nickel, palladium and platinum from co-ordinated phosphino-enolates: X-ray structures of (R,S)-cis-[Pd{Ph₂PCH[C(O)Ph][MeO₂CCC(CO₂Me)]}₂] and [(o-C₆H₄CH₂NMe₂)Pd{Ph₂PC{C(O)Ph][(MeO₂C)CC(H)(CO₂Me)]}]
  作者：Fadila Balegroune、Pierre Braunstein、Tânia Mara Gomes Carneiro、Daniel Grandjean、Dominique Matt

  DOI：10.1039/c39890000582

  日期：——

  polyfunctional phosphine ligands may be generated by carbon–carbon coupling between enolato complexes of the type [Ln[graphic omittd])Ph}](M = Ni, Pd, Pt) and the alkyne MeO2CCCCO2Me; the thermal isomerisation of the (P, alkenyl) form either leads to a (P, alkyl) chelate or, after metal–carbon bond cleavage and H-shift, to a ligand rearrangement with regeneration of (P, O) co-ordination.

  通过[L n [Graph omittd]）Ph}]（M = Ni，Pd，Pt）的烯醇配合物与炔烃MeO 2 CC CCO 2 Me之间的碳-碳偶合可以生成三个异构的多官能膦配体。（P，烯基）形式的热异构化要么导致（P，烷基）螯合，要么在金属-碳键断裂和H移位后，伴随（P，O）配位的再生而发生配体重排。
• Synthesis of a new bifunctional hemilabile ligand by insertion of PhNCO into a co-ordinated β-phosphinoketonate. Crystal structure of [(o-C₆H₄CH₂NMe₂)Pd(Ph₂PC[C(O)NHPh][C(Ph)O])]
  作者：Salah-Eddine Bouaoud、Pierre Braunstein、Daniel Grandjean、Dominique Matt、Dominique Nobel

  DOI：10.1039/c39870000488

  日期：——

  The air-stable complex [(o-[graphic omitted])Ph}](1) is an ambident reactive species which readily reacts with PhNCO affording the two isomers (2a)(title complex) and (2b) which formally result from insertion of isocyanate into the C-H bond of the phosphinoketonate; the resulting bifunctional phosphine ligand displays hemilabile character.

  在空气中稳定的络合物 [(o-[graphic omitted])Ph}](1) 是一种含混反应物，很容易与 PhNCO 发生反应，产生两种异构体 (2a)（标题络合物）和 (2b)，这两种异构体是异氰酸酯插入膦酮酸酯的 C-H 键的结果；由此产生的双官能团膦配体显示出血亲和特性。
• Braunstein, Pierre; Gomes Carneiro, Tânia Mara; Matt, Dominique, Organometallics, 1989, vol. 8, # 7, p. 1737 - 1743
  作者：Braunstein, Pierre、Gomes Carneiro, Tânia Mara、Matt, Dominique、Balegroune, Fadila、Grandjean, Daniel

  DOI：——

  日期：——
• Bouaoud, Salah-Eddine; Braunstein, Pierre; Grandjean, Daniel, Inorganic Chemistry, 1988, vol. 27, # 13, p. 2279 - 2286
  作者：Bouaoud, Salah-Eddine、Braunstein, Pierre、Grandjean, Daniel、Matt, Dominique、Nobel, Dominique

  DOI：——

  日期：——
• 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 <i>cis</i>-[Ni{Ph₂PCH C( O)(<i>p</i>-C₆H₄CH₃}₂]CoI₂
  作者：Jacques Andrieu、Pierre Braunstein、Marc Drillon、Yves Dusausoy、Florent Ingold、Pierre Rabu、Antonio Tiripicchio、Franco Ugozzoli

  DOI：10.1021/ic9513494

  日期：1996.1.1

  The chemoselective reactivity of metal-coordinated phosphino enolates has been studied by the reactions of cis-[NiR'(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)PdPh(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-[NiPh(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-[PtPh(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-[NiR'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)PdPh(2)PCH(sic)C((sic)O)Ph}] with [Au(PPh(3))](+) occurred with formation of [(dmba) PdPh(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.