RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(benzenethiolate)]CF3SO3 | 170551-79-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(benzenethiolate)]CF3SO3
• 英文别名: benzenethiolate;nickel(2+);1,4,8,11-tetramethyl-1,4,8,11-tetrazacyclotetradecane;trifluoromethanesulfonate
• CAS: 170551-79-8
• 化学式: CF₃O₃S*C₂₀H₃₇N₄NiS
• 分子量: 573.367
• InChiKey: LCWJOGXAPJEGPW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  2.15
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  79.5
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  碘乙烷 、 RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(benzenethiolate)]CF3SO3 以 四氢呋喃 、 乙腈 为溶剂， 生成 RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)I]CF3SO3
  参考文献：
  名称：

  Syntheses, Reactivity and Molecular Structures of RSRS-[Ni(tmc)SC6H5](PF6), RRSS-[Ni(tmc)SC6H5](CF3SO3) and RRSS-[Ni(tmc)](CF3SO3) (tmc = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane)

  摘要：

  The RSRS and RRSS isomers of [Ni(tmc)](OTf)2 (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; OTf(-) = CF3SO3-) react with NaSC6H5 to yield the corresponding high spin, five-coordinate derivatives, [Ni(tmc)SC6H5](OTf). The molecular structure of each has been determined by X-ray diffraction. RRSS-[Ni(tmc)SC6H5](OTf) crystallized in the monoclinic space group P2(1)/n, with a = 12.648(3) Angstrom, b = 15.145(4) Angstrom, c = 14.765(4) Angstrom, beta = 113.96(2)degrees, V = 2584(1) Angstrom(3), and Z = 4. The coordination sphere about Ni is best described as square pyramidal with a Ni-S bond distance of 2.369(2) Angstrom and Ni-N-av of 2.128 Angstrom. RSRS-[Ni(tmc)SC6H5]-(PF6) crystallized in the monoclinic space group P2(1)/n, with a = 13.037(5) Angstrom, b = 15.407(7) Angstrom, c = 13.706(7) Angstrom, beta = 113.53(3)degrees, V = 2524(2) Angstrom(3), and Z = 4. The Ni resides in a highly distorted square pyramid with a shorter Ni-S distance, 2.352(2)Angstrom and correspondingly longer Ni-N-av distance of 2.149 Angstrom. Alternatively [Ni(tmc)SR](OTf) may be produced by oxidative addition of disulfide, R(2)S(2) (R = C6H5, C2H5), to Ni(tmc)(OTf). The second-order rate constant, k(i), for reaction with (C6H5)(2)S-2 is 120 M(-1)s(-1). (C2H5)(2)S-2 reacts 5 orders of magnitude more slowly consistent with its greater S-S bond dissociation energy. The nickel thiolates react with haloalkanes, RX (RX = CH3I, C2H5I, (CH3)(2)CHI, C6H5CH2Cl), producing [Ni(tmc)X](OTf) and C(6)H(5)SR. The reaction is second order with k(2) decreasing in the order, CH3I > C2H5I > (CH3)(2)CHI. Strikingly, for reactions with a given RX, the RRSS isomer reacted ca. 350 times faster than the RSRS isomer. RRSS-[Ni(tmc)](OTf) Na(OTf) has also been characterized, having crystallized in the monoclinic space group C2/c, with a = 24.690(23) Angstrom, b = 11.261(5) Angstrom, c = 9.681(6) Angstrom, beta = 91.03(4)degrees, V = 2691(2) Angstrom(3), and Z = 4. The macrocycle provides the Ni(I) ion with a square planar coordination environment in which there are two distinct Ni-N bond distances, 2.120(5) and 2.095(5) Angstrom.

  DOI：

  10.1021/ic00127a029
• 作为产物：
  描述：

  二苯二硫醚 、 [Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)](OTf) 以 四氢呋喃 为溶剂， 生成 RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(benzenethiolate)]CF3SO3
  参考文献：
  名称：

  Syntheses, Reactivity and Molecular Structures of RSRS-[Ni(tmc)SC6H5](PF6), RRSS-[Ni(tmc)SC6H5](CF3SO3) and RRSS-[Ni(tmc)](CF3SO3) (tmc = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane)

  摘要：

  The RSRS and RRSS isomers of [Ni(tmc)](OTf)2 (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; OTf(-) = CF3SO3-) react with NaSC6H5 to yield the corresponding high spin, five-coordinate derivatives, [Ni(tmc)SC6H5](OTf). The molecular structure of each has been determined by X-ray diffraction. RRSS-[Ni(tmc)SC6H5](OTf) crystallized in the monoclinic space group P2(1)/n, with a = 12.648(3) Angstrom, b = 15.145(4) Angstrom, c = 14.765(4) Angstrom, beta = 113.96(2)degrees, V = 2584(1) Angstrom(3), and Z = 4. The coordination sphere about Ni is best described as square pyramidal with a Ni-S bond distance of 2.369(2) Angstrom and Ni-N-av of 2.128 Angstrom. RSRS-[Ni(tmc)SC6H5]-(PF6) crystallized in the monoclinic space group P2(1)/n, with a = 13.037(5) Angstrom, b = 15.407(7) Angstrom, c = 13.706(7) Angstrom, beta = 113.53(3)degrees, V = 2524(2) Angstrom(3), and Z = 4. The Ni resides in a highly distorted square pyramid with a shorter Ni-S distance, 2.352(2)Angstrom and correspondingly longer Ni-N-av distance of 2.149 Angstrom. Alternatively [Ni(tmc)SR](OTf) may be produced by oxidative addition of disulfide, R(2)S(2) (R = C6H5, C2H5), to Ni(tmc)(OTf). The second-order rate constant, k(i), for reaction with (C6H5)(2)S-2 is 120 M(-1)s(-1). (C2H5)(2)S-2 reacts 5 orders of magnitude more slowly consistent with its greater S-S bond dissociation energy. The nickel thiolates react with haloalkanes, RX (RX = CH3I, C2H5I, (CH3)(2)CHI, C6H5CH2Cl), producing [Ni(tmc)X](OTf) and C(6)H(5)SR. The reaction is second order with k(2) decreasing in the order, CH3I > C2H5I > (CH3)(2)CHI. Strikingly, for reactions with a given RX, the RRSS isomer reacted ca. 350 times faster than the RSRS isomer. RRSS-[Ni(tmc)](OTf) Na(OTf) has also been characterized, having crystallized in the monoclinic space group C2/c, with a = 24.690(23) Angstrom, b = 11.261(5) Angstrom, c = 9.681(6) Angstrom, beta = 91.03(4)degrees, V = 2691(2) Angstrom(3), and Z = 4. The macrocycle provides the Ni(I) ion with a square planar coordination environment in which there are two distinct Ni-N bond distances, 2.120(5) and 2.095(5) Angstrom.

  DOI：

  10.1021/ic00127a029