[1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]palladium(II) | 171523-38-9

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]palladium(II)
• 英文别名: [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato]palladium(II)；[1,5-bis(mercaptoethyl)1,5-diazacyclooctane]Pd
• CAS: 171523-38-9
• 化学式: C₁₀H₂₀N₂PdS₂
• 分子量: 338.834
• InChiKey: JLABOQMOBZOHDK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]palladium(II) 以 甲醇 、 乙醚 为溶剂， 生成 [1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II) * 3 H2O
  参考文献：
  名称：

  Metallosulfoxides and -sulfones: Sulfur Oxygenates of [1,5-Bis(2-mercaptoethyl)-1,5-diazacyclooctanato]palladium(II)

  摘要：

  Successive sulfur-site oxygenation of the dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato] palladium(II), Pd-1, using H2O2 as an O atom source produced all but one member of the series of palladium(II) complexes containing sulfinate (metallosulfone) and sulfenate (metallosulfoxide) S-donor ligands: the monosulfoxide, PdS(=O)R or Pd-4; bis(sulfoxide), Pd(S(=O)R)(2) or Pd-5; sulfone/sulfoxide, Pd(SO(2)R)S(=O)R or Pd-6; and the bis(sulfone) Pd(SO(2)R)(2) or Pd-3 complex. A unique site selectivity for the addition of a second O atom from H2O2 to thiolate sulfur of Pd-4 producing the bis(sulfoxide), Pd-5, exclusively, precluded the preparation of the monosulfone complex, Pd(SO(2)R)SR or Pd-2, via that route. However, the dithiolate Pd-1 reacts with O-2 photochemically in aprotic solvents, giving access to this last member of the series, Pd-2. Further reaction of Pd-2 with O-2 under UV photolysis gives the bis(sulfone) complex, Pd-3. The oxygenates were characterized by various spectroscopies, electrochemistry, and X-ray crystallography. Mass spectrometry delineated a single O atom loss pathway for the sulfoxide species, while SO2 and O-2 loss is found in sulfone cases. Electrochemical studies show that the addition of an O atom to a thiolate sulfur to create a sulfoxide S-donor results in a stabilization of the Pdl oxidation state in the range 50-70 mV, while the addition of an O atom to a sulfoxide sulfur to create a sulfone S-donor results in greater stabilization of the Pd-1 oxidation state in the range 190-220 mV. Complex Pd-2 crystallizes in the monoclinic P2(1)/c (No. 14) space group with a = 8.362(11) Angstrom, b = 12.102(9) Angstrom, c = 12.990(14) Angstrom, beta = 101.39(9)degrees, V = 1289(2) Angstrom(3) and Z = 4. Complex Pd-4 crystallizes in the orthorombic P2(1)2(1)2 space group with a 12.210(2) Angstrom, b = 15.931(4) Angstrom, c = 6.802(2) Angstrom, V = 1323.1(6) Angstrom(3), and Z = 4. Complex Pd-6 cocrystallizes with Pd-3 in the monoclinic C2/c space group with a 15.862(5) Angstrom, b = 8.146(2) Angstrom, c = 21.812(9) Angstrom, beta = 107.82(2)degrees, V = 2683(2) Angstrom(3), and Z = 8.

  DOI：

  10.1021/ic00129a012
• 作为产物：
  描述：

  [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato]palladium(II) * SO2 以 乙腈 为溶剂， 生成 [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]palladium(II)
  参考文献：
  名称：

  Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates

  摘要：

  The dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Pd(II), (bme-daco)Pd-II or Pd-1, whose structure was determined by X-ray crystallography (monoclinic P2(1)/m space group with a = 6.1680(10) Angstrom, b = 15.715(5) Angstrom, c = 6.5930(10) Angstrom, beta = 107.090(10)degrees, Z = 2, R = 0.0291, R(W) = 0.0718), has been added to a group of metal thiolates which form sulfur-site SO2 adducts. Exposure of the Pd-l complex to SO2 in methanol results in the precipitation of yellow/orange crystalline Pd-1 SO2: monoclinic space group, P2(1)/c (No. 14), with a 8.928(2) Angstrom, b = 14.655(4) Angstrom, c = 11.067(2) Angstrom, beta = 97.29(2)degrees, Z = 4, R = 0.0348, R(W) = 0.0944. Analogous thiolate-SO2 adducts based on (bme-daco)Ni-II, Ni-1 . SO2, (Ph(2)PCH(2)CH(2)S)(2)Ni-II, Ni-2 . SO2, and (bme*-daco)Ni-II, Ni-1*. SO2, also precipitate from methanol. To explore the transformation of SO2 to SO42- in these adducts, the following three factors expected to control the sulfate-forming reaction have been examined: (i) the stability of SO2 adducts; (ii) the oxidizability of the metal thiolate or its tendency to generate disulfide products on oxidation; and (iii) the ability of the metal thiolates to react with O-2 and produce sulfur-oxygenated products. The studies indicate that the last factor is the most important influence on SO2 oxygenation. A possible mechanism involves the transient formation of an SO2-stabilized sulfperoxide intermediate, which behaves as a nucleophile and further reacts with SO2 to produce SO42-. The use of the aforementioned metal thiolate complexes as catalysts for SO2 oxygenation in the presence of a sacrificial electron donor has also been explored; simple salts such as NiCl2 and NiSO4 are more efficient than the complexes.

  DOI：

  10.1021/ic00129a013
• 作为试剂：
  描述：

  二氧化硫 、 氧气 在 [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]palladium(II) NaSPh 作用下， 以 甲醇 为溶剂， 生成 硫酸酯
  参考文献：
  名称：

  Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates

  摘要：

  The dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Pd(II), (bme-daco)Pd-II or Pd-1, whose structure was determined by X-ray crystallography (monoclinic P2(1)/m space group with a = 6.1680(10) Angstrom, b = 15.715(5) Angstrom, c = 6.5930(10) Angstrom, beta = 107.090(10)degrees, Z = 2, R = 0.0291, R(W) = 0.0718), has been added to a group of metal thiolates which form sulfur-site SO2 adducts. Exposure of the Pd-l complex to SO2 in methanol results in the precipitation of yellow/orange crystalline Pd-1 SO2: monoclinic space group, P2(1)/c (No. 14), with a 8.928(2) Angstrom, b = 14.655(4) Angstrom, c = 11.067(2) Angstrom, beta = 97.29(2)degrees, Z = 4, R = 0.0348, R(W) = 0.0944. Analogous thiolate-SO2 adducts based on (bme-daco)Ni-II, Ni-1 . SO2, (Ph(2)PCH(2)CH(2)S)(2)Ni-II, Ni-2 . SO2, and (bme*-daco)Ni-II, Ni-1*. SO2, also precipitate from methanol. To explore the transformation of SO2 to SO42- in these adducts, the following three factors expected to control the sulfate-forming reaction have been examined: (i) the stability of SO2 adducts; (ii) the oxidizability of the metal thiolate or its tendency to generate disulfide products on oxidation; and (iii) the ability of the metal thiolates to react with O-2 and produce sulfur-oxygenated products. The studies indicate that the last factor is the most important influence on SO2 oxygenation. A possible mechanism involves the transient formation of an SO2-stabilized sulfperoxide intermediate, which behaves as a nucleophile and further reacts with SO2 to produce SO42-. The use of the aforementioned metal thiolate complexes as catalysts for SO2 oxygenation in the presence of a sacrificial electron donor has also been explored; simple salts such as NiCl2 and NiSO4 are more efficient than the complexes.

  DOI：

  10.1021/ic00129a013

文献信息

• Singlet Oxygen and the Production of Sulfur Oxygenates of Nickel(II) and Palladium(II) Thiolates
  作者：Craig A. Grapperhaus、Michael J. Maguire、Thawatchai Tuntulani、Marcetta Y. Darensbourg

  DOI：10.1021/ic970050d

  日期：1997.4.1

  acetonitrile and sulfoxides favored in methanol. There is also a ligand and metal effect. The proposed mechanistic pathways involving a persulfoxide precursor to single sulfur site O(2) addition (producing metallosulfones) and adjacent sulfur site O(2) addition (producing metallosulfoxides) are consistent with product distribution, comparison to the much studied oxygenation of organic sulfides, and previous

  二硫醇金属[1,5-双（2-巯基乙基）-1,5-二氮杂环辛烷]镍（II）（Ni-1），位阻类似物（Ni-1）和钯类似物Pd-1与之反应（1）Delta O（2）产生各种稳定且可分离的金属氯砜（MS（O（2））R）和金属氯亚砜（MS（O）R）。通过敏化剂Rose Bengal光化学产生单线态氧，并通过1,4-二甲基萘的1,4-内过氧化物分解产生热态单线态氧。O（2）从其基态（3）Sigma激发到激发态（1）Delta时，观察到速率增加和氧合产率增加。反应取决于溶剂和浓度，其中乙腈中通常优选砜，而甲醇中通常优选亚砜。还有配体和金属效应。