[1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato]nickel(II) | 152385-51-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato]nickel(II)
• 英文别名: [1,5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)；(N-N'-bis(2-sulfeno-2-methylpropyl)-1,5-dizacyclooctanato)nickel(II)
• CAS: 152385-51-8
• 化学式: C₁₄H₂₈N₂NiO₂S₂
• 分子量: 379.211
• InChiKey: IMENBFPBRLMOTJ-UHFFFAOYSA-N

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-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato]nickel(II) 以 甲醇 为溶剂， 生成 1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)nickel(II)
  参考文献：
  名称：

  Study of Sulfinate and Sulfenate Complexes Derived from the Oxygenation of Thiolate Sulfur in [1,5-Bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)

  摘要：

  A series of nickel(II) complexes containing sulfinate and sulfenate S-donor sites has been prepared from systematic oxygenations of the dithiolate complex [1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) ((bme*-daco)Ni, 1*) and the whole series characterized by mass spectrometry: and X-ray crystallography. The dithiolate complex reacts in organic solvents with molecular oxygen to produce sulfinate (NiS(O)(2)R) complexes, while reactions with hydrogen peroxide have, in addition,permitted the isolation of sulfenate (NiS(O)R) products. The X-ray crystal structures of the complexes [1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (2*), [1,5-bis(2-sulfino-2-methylpropyl)-1,5-diazacyclootanato-(2-)]nickel(II)) (3*), [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (5*), and [1-(2-sulfeno-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (6*) were determined and metric data compared with previously characterized 1* and 4*, [1-(2-mercapto-2-methylpropyl)-5-(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II). Analysis of the Ni-S-(av) bond distances for homoleptic complexes reveals that the bond distances are in the order Ni-S(O)R (2.167(5)) > Ni-SR (2.159(3)) > Ni-S(O)(2)R (2.127(3)). The average nickel sulfinate S-O distance at 1.459 Angstrom is ca. 0.1 Angstrom shorter than the average nickel sulfenate S-O distance at 1.545 Angstrom. These bond dimensions correlated well with spectroscopic and reactivity data. Electrochemical studies find the Ni-II/I reversible couple to be stabilized by ca. 100 mV with conversion of thiolate-S to sulfenate-S donor, while conversion of a sulfenate to a sulfinate stabilized the Ni-I state by an additional 200 mV. Mass spectrometry delineated O-atom loss pathways to dominate initial fragmentation patterns from the parent ions in the protic matrix thioglycerol; however, SO2 extrusion also occurs and is prominent in a nitrobenzyl alcohol (NBA) matrix. The sulfenate complexes are unexpectedly stable and do not undergo either inter- or intramolecular disproportionation reactions to thiolate and sulfinate, nor do they transfer oxygen to triphenyl- or tributylphosphine. Sulfur dioxide removed oxygen from the sulfenates, yielding thiolates and SO3, whereas no reaction occurred with the sulfinate complexes. Complexes that represent partial oxidation of the sulfurs further reacted with hydrogen peroxide to produce higher oxygenates and also reacted with electrophiles such as alkylhalides to produce S-bound sulfoxide ligands.

  DOI：

  10.1021/ja00108a013
• 作为产物：
  描述：

  N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane 以 甲醇 、 甲苯 为溶剂， 生成 [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato]nickel(II)
  参考文献：
  名称：

  Study of Sulfinate and Sulfenate Complexes Derived from the Oxygenation of Thiolate Sulfur in [1,5-Bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)

  摘要：

  A series of nickel(II) complexes containing sulfinate and sulfenate S-donor sites has been prepared from systematic oxygenations of the dithiolate complex [1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) ((bme*-daco)Ni, 1*) and the whole series characterized by mass spectrometry: and X-ray crystallography. The dithiolate complex reacts in organic solvents with molecular oxygen to produce sulfinate (NiS(O)(2)R) complexes, while reactions with hydrogen peroxide have, in addition,permitted the isolation of sulfenate (NiS(O)R) products. The X-ray crystal structures of the complexes [1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (2*), [1,5-bis(2-sulfino-2-methylpropyl)-1,5-diazacyclootanato-(2-)]nickel(II)) (3*), [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (5*), and [1-(2-sulfeno-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (6*) were determined and metric data compared with previously characterized 1* and 4*, [1-(2-mercapto-2-methylpropyl)-5-(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II). Analysis of the Ni-S-(av) bond distances for homoleptic complexes reveals that the bond distances are in the order Ni-S(O)R (2.167(5)) > Ni-SR (2.159(3)) > Ni-S(O)(2)R (2.127(3)). The average nickel sulfinate S-O distance at 1.459 Angstrom is ca. 0.1 Angstrom shorter than the average nickel sulfenate S-O distance at 1.545 Angstrom. These bond dimensions correlated well with spectroscopic and reactivity data. Electrochemical studies find the Ni-II/I reversible couple to be stabilized by ca. 100 mV with conversion of thiolate-S to sulfenate-S donor, while conversion of a sulfenate to a sulfinate stabilized the Ni-I state by an additional 200 mV. Mass spectrometry delineated O-atom loss pathways to dominate initial fragmentation patterns from the parent ions in the protic matrix thioglycerol; however, SO2 extrusion also occurs and is prominent in a nitrobenzyl alcohol (NBA) matrix. The sulfenate complexes are unexpectedly stable and do not undergo either inter- or intramolecular disproportionation reactions to thiolate and sulfinate, nor do they transfer oxygen to triphenyl- or tributylphosphine. Sulfur dioxide removed oxygen from the sulfenates, yielding thiolates and SO3, whereas no reaction occurred with the sulfinate complexes. Complexes that represent partial oxidation of the sulfurs further reacted with hydrogen peroxide to produce higher oxygenates and also reacted with electrophiles such as alkylhalides to produce S-bound sulfoxide ligands.

  DOI：

  10.1021/ja00108a013

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。
• Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates
  作者：Marcetta Y. Darensbourg、Thawatchai Tuntulani、Joseph H. Reibenspies

  DOI：10.1021/ic00129a013

  日期：1995.12

  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.
• Template Effect for O₂ Addition across <i>cis</i>-Sulfur Sites in Nickel Dithiolates
  作者：Craig A. Grapperhaus、Marcetta Y. Darensbourg、Lloyd W. Sumner、David H. Russell

  DOI：10.1021/ja953489i

  日期：1996.1.1
• Font, Ivan; Buonomo, Rizalia; Reibenspies, Joseph H., Inorganic Chemistry, 1993, vol. 32, # 26, p. 5897 - 5898
  作者：Font, Ivan、Buonomo, Rizalia、Reibenspies, Joseph H.、Darensbourg, Marcetta Y.

  DOI：——

  日期：——