(1,2-bis(diphenylphosphino)benzene)(maleonitriledithiolato)nickel(II) | 151138-44-2

• 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: (1,2-bis(diphenylphosphino)benzene)(maleonitriledithiolato)nickel(II)
• CAS: 151138-44-2
• 化学式: C₃₄H₂₄N₂NiP₂S₂
• 分子量: 645.347
• InChiKey: CAHCLJCMEXYJFP-LWFKIUJUSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.84
• 重原子数：
  41.0
• 可旋转键数：
  4.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.58
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (1,2-bis(diphenylphosphino)benzene)nickel diiodide 、 disodium cis-1,2-dicyano-1,2-ethylenedithiolate 以 甲醇 、 二氯甲烷 为溶剂， 生成 (1,2-bis(diphenylphosphino)benzene)(maleonitriledithiolato)nickel(II)
  参考文献：
  名称：

  Star porphyrazines: peripheral chelation of porphyrazineoctathiolate by diphosphinonickel ions

  摘要：

  We have synthesized new pentametallic macrocyclic complexes based on the polynucleating ligand, porphyrazine-2,3,7,8,12,13,17,18-octathiolate, (pzot)8-. This ligand can be thought of as a porphyrazine (tetraazaporphyrin) bearing four dithiolene moieties peripherally at the beta-pyrrole positions, and we show that a transition-metal ion can be chelated to each of the four peripheral dithiolene moieties. The complexes [(P-P)Ni]4[Ni(pzot)] (2a, P-P = dppe; 2b, P-P = dppy; 2c, P-P = dppb; 2d, P-P = dcpe) have been synthesized and characterized. Complex 2a crystallizes in the orthorhombic space group Cmc2(1) (No. 36) with 4 macrocycles and 16 solvent molecules (N,N-dimethylformamide) in a unit cell of dimensions a = 24.630(5) angstrom, b = 20.607(4) angstrom, c = 30.675(6) angstrom. The [Ni(pzot)]8- ligand in 2a coordinates four Ni(P-P) moieties around its periphery with the two thiolate sulfur atoms of each pyrrole binding a nickel ion in a bidentate (S-S) coordination mode. This is in contrast to the reaction of [Ni(pzot)]8- with SnR2X2, which yielded Ni(pzot)(SnR2)4 (1), where each tin is coordinated in the tridentate (S-N-S) mode, with the thiolate sulfur atoms from two pyrroles and one m-nitrogen atom as ligands from the macrocycle (Velazquez, C. S.; Fox, G. A.; Broderick, W. E.; Andersen, K; Anderson, O. P.; Barrett, A. G. M.; Hoffman, B. M. J. Am. Chem. Soc. 1992, 114, 7416-7424). Comparison of the crystal structures of 1,2a, and aquo(octakis(methylthio)porphyrazinato)magnesium(II) (Mg(omtp)), a structurally unconstrained reference compound with eight peripheral methylthio groups, shows that [Ni(pzot)]8- adjusts to accommodate either the (S-S) or (S-N-S) modes of coordinating the metal ions at the periphery by a swing of the C(beta)-S bond. H-1 and P-31 NMR studies have been used to determine the nature of the coordination of the Ni(P-P) units to the [Ni(pzot)]8- macrocycle in solution. Model compounds were synthesized as structural references to mimic both possible coordination sites of the [Ni(pzot)]8- ligand. The H-1 and P-31 NMR chemical shifts of macrocycles 2a-d and their respective bidentate model complexes clearly indicate that the macrocycle in solution also binds the Ni(P-P) units in a bidentate fashion. The electronic absorption spectra of complexes 2a-d show a red-shift of the absorbance in the Q-band region due to interaction of the porphyrazine pi-system with the four peripheral metal ions.

  DOI：

  10.1021/ja00075a016

文献信息

• Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers
  作者：Kuppuswamy Arumugam、Malathy Selvachandran、Antony Obanda、Mohamed C. Shaw、Perumalreddy Chandrasekaran、Sonya L. Caston Good、Joel T. Mague、Stephen Sproules、James P. Donahue

  DOI：10.1021/acs.inorgchem.8b00201

  日期：2018.4.2

  Compounds of the type [(S2C2R2)M(μ-tpbz)M(S2C2R2)] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(S2C2R2)SnR′2] reagents, by direct displacement of dithiolene ligand from [M(S2C2R2)2] with 0.5 equiv of tpbz, or by salt metathesis using Na2[S2C2(CN)2] in conjunction with X2M(μ-tpbz)MX2 (X = halide). X-ray crystallography

  [[（S 2 C 2 R 2）M（μ-tpbz）M（S 2 C 2 R 2）]类型的化合物（R = CN，Me，Ph，对-茴香基； M = Ni，Pd，Pt； tpbz = 1,2,4,5-四（二苯基膦基）苯）已经制备通过转移金属化与[（S 2 c ^ 2 - [R 2）SNR' 2 ]的试剂，通过从二硫配体的直接置换[M（S 2 ç含0.5当量的tpbz的2 R 2）2 ]，或使用Na 2 [S 2 C 2（CN）2]与X 2 M（μ-tpbz）MX 2（X =卤化物）结合使用。X射线晶体学揭示了（S 2 C 2）M（P 2 C 6 P 2）M（S 2 C 2）核的一系列拓扑结构（起伏，椅子，弓形）。[（S 2 C 2 R 2）M（μ-tpbz）M（S 2 C 2 R 2）]（R = Me，Ph，p-茴香基）化合物支持可逆或准可逆氧化，与二硫代苯并发氧化同时进行烯1,2-二硫代酸酯到自由基单阴离子的末端配体，形成[（-小号•