[Pt(SH)2(o-bis(diphenylphosphinomethyl)benzene)] | 1027104-99-9

• 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: [Pt(SH)2(o-bis(diphenylphosphinomethyl)benzene)]
• CAS: 1027104-99-9
• 化学式: C₃₂H₃₀P₂PtS₂
• 分子量: 735.75
• InChiKey: UCAHLXJKRDNKGO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.41
• 重原子数：
  37.0
• 可旋转键数：
  4.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (η-pentamethylcyclopentadienyl)(nitrosyl)dichlorotungsten 、 二氯甲烷 、 [Pt(SH)2(o-bis(diphenylphosphinomethyl)benzene)] 在 triethylamine 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到[(o-bis(diphenylphosphinomethyl)benzene)Pt(μ-S)2W(NO)(η5-C5Me5)]*Et2O*0.5CH2Cl2
  参考文献：
  名称：

  Synthesis, Structures, and Properties of Group 9− and Group 10−Group 6 Heterodinuclear Nitrosyl Complexes

  摘要：

  The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)(2)(PMe3)] (M = Rh, Ir; Cp* = eta(5)-C5Me5) with the group 6 nitrosyl complexes [CP*M'Cl-2(NO)] (M' = Mo", W) in the presence of NEt3 affords a series of bis(sulfido)bridged early-late heterobimetallic (ELHB) complexes [CP*M(PMe3)(mu-S)(2)M'(NO)Cp*] (2a, M = Rh, M' = Mo; 2b, M = Rh, M' = W; 3a, M = Ir, M' = Mo; 3b, M = Ir, M' = W). Similar reactions of the group 10 bis(hydrosulfido) complexes [M(SH)(2)(dppe)] (M = Pd, Pt; dppe = Ph2P(CH2)(2)PPh2), [Pt(SH)(2)(dppp)] (dppp = Ph2P(CH2)(3)Pph(2)), and [M(SH)(2)(dpmb)] (dpmb = o-C6H4(CH2PPh2)(2)) give the group 10-group 6 ELHB complexes [(dppe)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M'= Mo, W), [(dppp)Pt(mu-S)(2)M'(NO)Cp*] (6a, M'= Mo; 6b, M'= W), and [(dpmb)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M' = Mo, W), respectively. Cyclic voltammetric measurements reveal that these ELHB complexes undergo reversible one-electron oxidation at the group 6 metal center, which is consistent with isolation of the single-electron oxidation products [Cp*M(PMe3)(mu-S)(2)M'(NO)Cp*][PF6] (M = Rh, Ir; M' = Mo, W). Upon treatment of 2b and 3b with ROTf (R = Me, Et; OTf = OSO(2)CFA the 0 atom of the terminal nitrosyl ligand is readily alkylated to form the alkoxyimido complexes such as [Cp*Rh(PMe3)(mu-S)(2)W(NOMe)Cp*][OTf]. In contrast, methylation of the Rh-, Ir-, and Pt-Mo complexes 2a, 3a, and 6a results in S-methylation, giving the methanethiolato complexes [Cp*M(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*][BPh4] (M = Rh, Ir) and [(dppp)Pt(mu-SMe)(mu-S)Mo(NO)Cp*][OTf], respectively. The Pt-W complex 6b undergoes either S- or O-methylation to form a mixture of [(dppp)Pt(mu-SMe)(mu-S)W(NO)Cp*][OTf] and [(dppp)Pt(mu-S)(2)W(NOMe)Cp*][OTf]. These observations indicate that O-alkylation and one-electron oxidation of the dinuclear nitrosyl complexes are facilitated by a common effect, i.e., donation of electrons from the group 9 or 10 metal center, where the group 9 metals behave as the more effective electron donor.

  DOI：

  10.1021/ic702309h
• 作为产物：
  描述：

  sodium hydrogen sulfide 、 (α,α-bis(diphenylphosphanyl)-o-xylene)dichloridoplatinum(II) 以 乙醇 、 苯 为溶剂， 以80%的产率得到[Pt(SH)2(o-bis(diphenylphosphinomethyl)benzene)]
  参考文献：
  名称：

  Synthesis, Structures, and Properties of Group 9− and Group 10−Group 6 Heterodinuclear Nitrosyl Complexes

  摘要：

  The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)(2)(PMe3)] (M = Rh, Ir; Cp* = eta(5)-C5Me5) with the group 6 nitrosyl complexes [CP*M'Cl-2(NO)] (M' = Mo", W) in the presence of NEt3 affords a series of bis(sulfido)bridged early-late heterobimetallic (ELHB) complexes [CP*M(PMe3)(mu-S)(2)M'(NO)Cp*] (2a, M = Rh, M' = Mo; 2b, M = Rh, M' = W; 3a, M = Ir, M' = Mo; 3b, M = Ir, M' = W). Similar reactions of the group 10 bis(hydrosulfido) complexes [M(SH)(2)(dppe)] (M = Pd, Pt; dppe = Ph2P(CH2)(2)PPh2), [Pt(SH)(2)(dppp)] (dppp = Ph2P(CH2)(3)Pph(2)), and [M(SH)(2)(dpmb)] (dpmb = o-C6H4(CH2PPh2)(2)) give the group 10-group 6 ELHB complexes [(dppe)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M'= Mo, W), [(dppp)Pt(mu-S)(2)M'(NO)Cp*] (6a, M'= Mo; 6b, M'= W), and [(dpmb)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M' = Mo, W), respectively. Cyclic voltammetric measurements reveal that these ELHB complexes undergo reversible one-electron oxidation at the group 6 metal center, which is consistent with isolation of the single-electron oxidation products [Cp*M(PMe3)(mu-S)(2)M'(NO)Cp*][PF6] (M = Rh, Ir; M' = Mo, W). Upon treatment of 2b and 3b with ROTf (R = Me, Et; OTf = OSO(2)CFA the 0 atom of the terminal nitrosyl ligand is readily alkylated to form the alkoxyimido complexes such as [Cp*Rh(PMe3)(mu-S)(2)W(NOMe)Cp*][OTf]. In contrast, methylation of the Rh-, Ir-, and Pt-Mo complexes 2a, 3a, and 6a results in S-methylation, giving the methanethiolato complexes [Cp*M(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*][BPh4] (M = Rh, Ir) and [(dppp)Pt(mu-SMe)(mu-S)Mo(NO)Cp*][OTf], respectively. The Pt-W complex 6b undergoes either S- or O-methylation to form a mixture of [(dppp)Pt(mu-SMe)(mu-S)W(NO)Cp*][OTf] and [(dppp)Pt(mu-S)(2)W(NOMe)Cp*][OTf]. These observations indicate that O-alkylation and one-electron oxidation of the dinuclear nitrosyl complexes are facilitated by a common effect, i.e., donation of electrons from the group 9 or 10 metal center, where the group 9 metals behave as the more effective electron donor.

  DOI：

  10.1021/ic702309h