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Asymmetric by Design: Heteroleptic Coordination Compounds with Redox-Active Dithiolene and 1,2,4,5-Tetrakis(isopropylthio)benzene Ligands
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-12-22 , DOI: 10.1021/acs.inorgchem.3c02928 Che Wu 1 , Lakshmi Nishanth Kakarla 2 , Chandru P. Chandrasekaran 2 , Xiaodong Zhang 1 , Joel T. Mague 1 , Stephen Sproules 3 , James P. Donahue 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-12-22 , DOI: 10.1021/acs.inorgchem.3c02928 Che Wu 1 , Lakshmi Nishanth Kakarla 2 , Chandru P. Chandrasekaran 2 , Xiaodong Zhang 1 , Joel T. Mague 1 , Stephen Sproules 3 , James P. Donahue 1
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The 1,2,4,5-tetrakis(alkylthio)benzenes are redox-active organosulfur molecules that support oxidation to a stable radical cation. Their utility as ligands for the assembly of multimetal complexes with tailored functionality/property is unexamined. Here, 1,2,4,5-tetrakis(isopropylthio)benzene (tptbz, 1) is shown to bind PdCl2 at either one end, leaving the other open, or at both ends to form centrosymmetric [Cl2Pd(tptbz)PdCl2], 4. Ligand metathesis between Na2[(N≡C)2C2S2] (Na2mnt) and [Cl2M(tptbz)] (M = Pd, 2; M = Pt, 3) yields [(mnt)M(tptbz)] (M = Pd, 5; M = Pt, 6), but an alternative route involving transmetalation with [(mnt)SnMe2] delivers substantially greater yield. The mixed dithiolene-dithioether compound [(Ph2C2S2)Pt(tptbz)] (8) is formed by a similar transmetalation protocol using [(Ph2C2S2)SnnBu2]. Compounds 5, 6, and 8 are the first such heteroleptic complexes prepared by deliberate synthesis. The cyclic voltammetry of 8 reveals anodic waves at +0.14 and +0.97 V vs Fc+/Fc, which are attributed to successive dithiolene oxidation processes. While oxidized at +0.73 V as a free ligand, the redox-active MO of tptbz is pushed to a higher potential upon coordination to Pt2+ and is inaccessible. Calculations of the structures of [8]+ and of [((Cl2-3,5-C6H3)2C2S2)Pt(tptbz)]+ show that, in the latter, the dithiolene MOs are drawn down in energy into proximity with the tptbz MOs.
中文翻译：
不对称设计：具有氧化还原活性二硫醇和 1,2,4,5-四(异丙硫基)苯配体的杂配位化合物
1,2,4,5-四（烷硫基）苯是氧化还原活性有机硫分子，支持氧化成稳定的自由基阳离子。它们作为具有定制功能/性质的多金属配合物组装的配体的实用性尚未得到检验。这里，1,2,4,5-四(异丙硫基)苯(tptbz, 1 )显示在任一端结合PdCl 2 ，使另一端开放，或在两端形成中心对称的[Cl 2 Pd(tptbz) PdCl 2 ]，4。Na 2 [(N≡C) 2 C 2 S 2 ] (Na 2 mnt) 和 [Cl 2 M(tptbz)] (M = Pd, 2 ; M = Pt, 3 )之间的配体复分解产生 [(mnt)M (tptbz)] (M = Pd, 5 ; M = Pt, 6 )，但涉及用 [(mnt)SnMe 2 ]进行金属转移的替代途径可提供显着更高的产率。混合二硫醇烯-二硫醚化合物[(Ph 2 C 2 S 2 )Pt(tptbz)] ( 8 )通过使用[(Ph 2 C 2 S 2 )Sn n Bu 2 ]的类似金属转移方案形成。化合物5、6和8是第一个通过精心合成制备的杂配配合物。8的循环伏安法显示相对于 Fc + /Fc 为 +0.14 和 +0.97 V 的阳极波，这归因于连续的二硫醇氧化过程。当作为游离配体在 +0.73 V 下被氧化时，tptbz 的氧化还原活性 MO 在与 Pt 2+配位后被推向更高的电位，并且难以接近。[ 8 ] +和 [((Cl 2 -3,5-C 6 H 3 ) 2 C 2 S 2 )Pt(tptbz)] +结构的计算表明，在后者中，绘制了二硫醇烯 MO能量下降至接近 tptbz MO。
更新日期：2023-12-22
中文翻译：
不对称设计：具有氧化还原活性二硫醇和 1,2,4,5-四(异丙硫基)苯配体的杂配位化合物
1,2,4,5-四（烷硫基）苯是氧化还原活性有机硫分子，支持氧化成稳定的自由基阳离子。它们作为具有定制功能/性质的多金属配合物组装的配体的实用性尚未得到检验。这里，1,2,4,5-四(异丙硫基)苯(tptbz, 1 )显示在任一端结合PdCl 2 ，使另一端开放，或在两端形成中心对称的[Cl 2 Pd(tptbz) PdCl 2 ]，4。Na 2 [(N≡C) 2 C 2 S 2 ] (Na 2 mnt) 和 [Cl 2 M(tptbz)] (M = Pd, 2 ; M = Pt, 3 )之间的配体复分解产生 [(mnt)M (tptbz)] (M = Pd, 5 ; M = Pt, 6 )，但涉及用 [(mnt)SnMe 2 ]进行金属转移的替代途径可提供显着更高的产率。混合二硫醇烯-二硫醚化合物[(Ph 2 C 2 S 2 )Pt(tptbz)] ( 8 )通过使用[(Ph 2 C 2 S 2 )Sn n Bu 2 ]的类似金属转移方案形成。化合物5、6和8是第一个通过精心合成制备的杂配配合物。8的循环伏安法显示相对于 Fc + /Fc 为 +0.14 和 +0.97 V 的阳极波，这归因于连续的二硫醇氧化过程。当作为游离配体在 +0.73 V 下被氧化时，tptbz 的氧化还原活性 MO 在与 Pt 2+配位后被推向更高的电位，并且难以接近。[ 8 ] +和 [((Cl 2 -3,5-C 6 H 3 ) 2 C 2 S 2 )Pt(tptbz)] +结构的计算表明，在后者中，绘制了二硫醇烯 MO能量下降至接近 tptbz MO。
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