trans-[Pd(CH(SC6H4Me-4)C6H(SC6H4Me-4)-2-(OMe)3-3,4,5)I(CN-2,6-dimethylphenyl)2] | 680580-63-6

• 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: trans-[Pd(CH(SC6H4Me-4)C6H(SC6H4Me-4)-2-(OMe)3-3,4,5)I(CN-2,6-dimethylphenyl)2]
• CAS: 680580-63-6
• 化学式: C₄₂H₄₃IN₂O₃PdS₂
• 分子量: 921.272
• InChiKey: YWQOQEMMAHIXEB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [Pd2(k2-C,S-CH(STol-p)(C6H(STol-p-2)(OMe)3-3,4,5))2(μ-I)2] 、 2,6-二甲基苯基异腈 以 二氯甲烷 为溶剂， 以61%的产率得到trans-[Pd(CH(SC6H4Me-4)C6H(SC6H4Me-4)-2-(OMe)3-3,4,5)I(CN-2,6-dimethylphenyl)2]
  参考文献：
  名称：

  Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes

  摘要：

  The arylmercurial [Hg{C6H3(CHO)(2)-2,5}Cl] (1) reacts with CH(OMe)(3) or HS(CH2)(2)SH to give [Hg{C6H3{CH(OMe)(2)}(2)-2,5}Cl] (2) or [Hg(Ar-a)Cl] [Ar-a = C6H3{CH(SCH2CH2S)}(2)-2,5 (3a)], respectively. The mercurial 2 or 3a reacts with (NMe4)(2)[Pd2Cl6] and 2,2'-bipyridine (bpy) or with trans- [PdCl2(PPh3)(2)] to give the aryl-palladium complex [Pd{C6H3{CH(OMe)(2)}(2)-2,5}Cl(bpy)] (4) or [Pd(kappa(2)-C,S-Ar-a)Cl(PPh3)] (5a*), respectively. The reaction of 1 with NaI3 renders IC6H3(CHO)(2)-2,5 (6), which reacts with HS(CH2)(2)SH to give IAra (7a). Similarly, IC6H(OMe)(3)-2,3,4-(CHO)-6 (8) reacts with HS(CH2)(2)SH or ToSH (To = C6H4Me-4) to give the corresponding dithioacetals IAX(b) [Ar-b = C6H(OMe)(3)-2,3,4-{CH(SCH2CH2S)}-6 (7b)] or IC6H(OMe)(3)-2,3,4-CH(STo)(2)-6 (9). The iodoarene 7a or 7b adds oxidatively to "Pd(dba)(2)" (dba = dibenzylideneacetone) to give [Pd(kappa(2)-C, S-Ar)(mu-I)](2) [Ar = Ar-a (10a), Ar-b (10b)], which, in turn, reacts (i) with 1 equiv of PPh3 to give [Pd(kappa(2)-C,S-Ar)I(PPh3)] [Ar = Ar-a (5a), Ar-b (5b)], (ii) with Tl(TfO) (TfO = CF3SO3) and PPh3 (1:2:4 molar ratio) to give [Pd(kappa(2)-C, S-Ar-b)(PPh3)(2)]TfO (11b), or (iii) with 1 equiv of Tl(TfO) and bpy (1:2:2 molar ratio) to give [Pd(kappa(2)-C, S-Arb)(bpy)]TfO (11b*). Complexes 10 react with 1 equiv of isonitriles to give, after a short period of reaction, the complexes [Pd(kappa(2)-C,S-Ar)I(CNR)] [Ar = Ar-a, R = Xy = 2,6-dimethylphenyl (12a), Bu-t (12a'); Ar = Ar-b, R = Bu-t (12b')]. The iminoacyl complexes [Pd(kappa(2)-C,S-Im)(mu-I](2) [Im = Im(a) (13a), Im(b) (13b)] can be obtained by stirring a solution of 12a for 5 days to give 13a or by reacting 10b with XyNC in 1:1 molar ratio during 22 h to give 13b. Complexes 10 react with 2 equiv of isonitriles to give the iminoacyl complexes [Pd(kappa(2)-C,S-Im)l(CNR)] [Im = C(=NR)C6H3-{CH(SCH2CH2S)}(2)-2,5, R = Xy, Im = Im(a) (14a), R = Bu-t, Im = Im(a')(14a'); Im = C(=NR)C6H(OMe)(3)-2,3,4-(SCH2CH2S)-6, R = Xy, Im = Im(b) (14b), R = Bu-t, Im = Im(b)' (14b')]. Complexes 14a,b react with 10a,b in 2:1 molar ratio to give 13a,b. Complexes 10a,b react with XyNC and Tl(TfO) (1:4:1) to give the dimeric cations [Pd{(kappa(2)-C,S-Im)(CNXy)}(2)(mu-I)]TfO [R = Xy, Im = im(a) (15a), Im(b) (15b)].The compound [Pd{kappa(2)-C,S-Ar-c}(mu-I)](2) (16) reacts (i) with PPh3 and Tl(TfO) in 1:4:2 molar ratio to give [Pd-II(kappa(2)-C,S-Ar-c)(PPh3)(2)]TfO <----> [Pd-0{eta(2)-kappa(3)-C,S,S-S(To)=CHC6H(STo)-2-(OMe)(3)-3,4,5}(PPh3)(2)]TfO (17), (ii) with isonitriles in 1:2 or 1:4 molar ratio yielding complexes [Pd(kappa(2)-C,S-Ar-c)I(CNR)] [R = Xy (18), R = Bu-t (18')] or trans-[Pd(kappa(1)-C-Ar-c)I(CNR)(2)] [R = Xy (19), R = Bu-t (19')], respectively, and (iii) with PPh3 in 1:2 molar ratio yielding [Pd(kappa(2)-C,S-Ar-c)I(PPh3)] (20). The iodoarene 9 reacts with Pd(dba)(2) (i) and PPh3 (1:1:1 molar ratio) to give [Pd{kappa(2)-C,S-Ar-c)I(PPh3)] [Ar-c = CH(STo)C6H(STo)-2-(OMe)(3)-3,4,5(20)] and (ii) PPh3 and Tl(TfO) (1: 1:2:1 molar ratio) to give 17. The crystal and molecular structures of 4, 5a*, 14a, and 14b have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om0342964