INORGANIC SULFUR CYCLE ON DINUCLEAR RHODIUM COMPLEX

双核铑络合物上的无机硫循环

• 批准号: 13440200
• 负责人: ISOBE Kiyoshi
• 金额: $ 10.37万
• 依托单位: KANAZAWA UNIVERSITY (2003)Osaka City University (2001-2002)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440200/
• 关键词: Inorganic Sulfur Cycle; Dinuclear Rhodium Complexes; Disulfido; Oxysulfido Complexes; Reduction of Sulfur Oxides; Thiolsulfonato Complexes; α-Disulfone Complexes; α-Disulfoxido Complexes; C-Cl結合の活性化; ジチオカルボキシラト錯体; 結晶相可逆異性化反応; ロジウム二核錯体; S-S結合挿入

Inorganic sulfur species with oxidation states between -2 and +6 have been isolated as the ligands in the rhodium dinuclear complexes from the oxygenation of disulfido complex [(RhCp^*)_2(μ-CH_2)_2(μ-S_2)] (1)with O_2 in the air. The isolated oxysulfur complexes are the thiolsulfinato complex [(RhCp^*)_2(μ-CH_2)_2(μ-SSO)] (2),thiolsulfonato complex [(RhCp^*)_2(μ-CH_2)_2(μ-SS(O)_2)] (3),α-disulfoxido complex cis-[(RhCp^*)_2(μ-CH_2)_2(μ-S(O)SO)] (4),and traps-[(RhCp^*)_2(μ-CH_2)_2(μ-S(O)SO)] (5).Using peroxides such as m-CPBA, complex 1 as well as 2 and 3 gave the α-disulfone complex [(RhCp^*)_2(μ-CH_2)_2(μ-S(O)_2SO_2)] (6).These dinuclear complexes have a dithiodirhodium metalacycle framework where the S-S moiety coordinates to the Rh-Rh group in a side-on fashion. The strong electron donation group of Cp^*Rh-RhCp^* allows the high grade oxygenated sulfur species of α-disulfone to work still as the didentate ligand through both S atoms. In this research the reactivity of the isolated oxysulfur complexes towards electrophiles and nucleophiles has been explored. Complex 6 is readily reduced to 3 by NaBH_4, not to 1. Although we did not succeed yet in the reduction of 3 to 1, but found that the reaction of 3 with I_2 or ICH_2CH_2I produces the precursor of 1, [{(RhCp^*)_2(μ-CH_2)_2}_2(μ_4-S_4)]^<2+>. The artificial sulfur cycle on the Rh-Rh bond is completed.

在二硫键配合物[（RhCp^*）_2（μ-CH_2）_2（μ-S_2）]（1）与O_2的氧化反应中，分离出了氧化态在-2 ~+6之间的无机硫物种。硫氧化合物为硫代亚磺酸根配合物[（RhCp^*）_2（μ-CH_2）_2（μ-SSO）]（2），硫代磺酸根配合物[（RhCp^*）_2（μ-CH_2）_2（μ-SS（O）_2）]（3），α-二亚砜配合物cis-[（RhCp^*）_2（μ-CH_2）_2（μ-S（O）SO）]（4），和捕获剂-[（RhCp^*）_2（μ-CH_2）_2（μ-S（O）SO）]（5）。配合物1、配合物2和配合物3得到了α-二砜配合物[（RhCp^*）_2（μ-CH_2）_2（μ-S（O）_2SO_2）]（6）。S部分以侧面方式与Rh-Rh基团配位。Cp^*Rh-RhCp^* 的强给电子基团允许α-二砜的高级氧化硫物质通过两个S原子仍然作为二齿配体起作用。在这项研究中，分离的氧硫配合物对亲电和亲核试剂的反应性进行了探索。配合物6容易被NaBH_4还原为3，而不是1。虽然我们尚未成功地将3还原为1，但发现3与I_2或ICH_2CH_2I反应产生1的前体[{（RhCp^*）_2（μ-CH_2）_2}_2（μ_4-S_4）]^<2+>。Rh-Rh键上的人工硫循环完成。

项目成果

Synthesis and behavior in solution of the triple cubane- and windmill-type framework isomers of an organorhodium tungsten oxide cluster [(Cp*Rh)4W4O16]

• DOI: 10.1002/aoc.447
• 发表时间: 2003-06-01
• 期刊: APPLIED ORGANOMETALLIC CHEMISTRY
• 影响因子: 3.9
• 作者: Nishikawa, K;Kido, K;Isobe, K
• 通讯作者: Isobe, K

Cesium(I)-mediated 3-D superstructures by one-pot self-organization of hydrogen-bonded nickel complexes.

• DOI: 10.1021/ic010331s
• 发表时间: 2001-10
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: M. Tadokoro;T. Shiomi;K. Isobe;K. Nakasuji

meso-Tetraphenylporphyrin Having Hexamaltosyl and Decyl Chain as an Amphiphilic Photosensitizer toward Photodynamic Therapy

具有六麦芽糖基和癸基链的内消旋四苯基卟啉作为光动力疗法的两亲性光敏剂

• 发表时间: 2002
• 期刊: Chem. Lett. 31
• 作者: A.Hamazawa

Tarlok Singh Lobana: "Activation of C-Cl and C-H Bonds by Ligated S_2^<2-> Ions : Conversion of Organic Chlorides into Organosulfur Compounds in cis[(IrCp^*)_2(μ-CH_2)_2(μ-S_2R)]^+"Angew.Chem.Int.Ed.. 43巻・2号. 213-215 (2004)

Tarlok Singh Lobana：“通过连接的 S_2^<2-> 离子激活 C-Cl 和 C-H 键：将有机氯化物转化为顺式有机硫化合物[(IrCp^*)_2(μ-CH_2)_2(μ-S_2R)” ]^+“Angew.Chem.Int.Ed..第 43 卷，第 2 期。213-215 (2004)

Kiyoshi Isobe: "Polyoxometalate Chemistry for Nano-composite Design ed. by T.Yamase. M.T.Pope"Kluwer Academic/Plenum Publishers, New York. 235 (2002)

Kiyoshi Isobe：“用于纳米复合材料设计的多金属氧酸盐化学，T.Yamase. M.T.Pope 编辑”，Kluwer 学术/Plenum 出版社，纽约。