Rational Synthesis of Dynamic Complexes of Mezzoscopic-size

介观尺寸动态配合物的合理合成

• 批准号: 14078211
• 负责人: TATSUMI Kazuyuki
• 金额: $ 40.9万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078211/
• 关键词: Dynamic Complexes; Rational Synthesis; Mezzoscopic; Thiolate Complexes; Metal Cluster; Metalloenzymes Model; Nitrogenase; Hydrogenase; 鉄硫黄クラスター; P-クラスター; FeMo-co; チオラート; スルフィド; 鉄; モリブデン; タングステン; 金属酵素; チオラート錯体; ニッケル; 無機ポリマー; クラスター; 環状ク

1. Rational Assemblage of Iron and Nickel Ions by Thiolate/thioether Hybrid Ligands Thiolate-sulfurs are coordinated at transition metal atoms strongly, while thioether-type sulfurs form weak M-S bonds, often exhibiting a facile association/dissociation equilibration. We have utilized the thiolate/thioether hybrid ligands RSCH_2CH_2S(-) (R=Et (etet), R=^iPr (ptet), R=Ph (ptet)) to assemble iron(II) and Ni(II) metal ions. For instance, the reaction of NiCl_2 with 2 equiv of Li(etet) produced a linear polymer [Ni(etet)_2]n, while the analogous 1 : 2 NiCl_/Li(ptet) reaction resulted in formation of a cyclic hexa-nuclear [Ni_6(ptet)_<12>]. In these mezzozcopic-size clusters/polymers, thiolate-sulfur atoms bridge Ni centers, leaving thioether sufurs uncoordinated. When the 1 : 1 mixture of NaSCH_2CH_2SR (R=Me (mtet), R=Et (etet), or R=^iPr (^iptet)) and NaS^tBu was treated with 1 equiv of NiCl_2, unusual cyclic deca-nuclear clusters [Ni(SCH_2CH_2SR)(S^tBu)_<10> were formed, where a solvent … More benzene/THF molecule was incorporated in the cavity of the ring for R=Et, ^iPr.2. Toward Better Iron-Sulfur Clusters Modeling the Nitrogenase Active Sites : The unusual [8Fe-7S] inorganic core structure of the reduced form of P-cluster (P^N) was self-assembled by the reaction of Fe{N(SiMe_3)_2}_2, tetramethylthiourea (tmtu), 2, 4, 6-triiso-propylbenzenethiol(HS-tip), and elemental sulfur in the ratio of 8(Fe) : 3(tmtu) : 12(HS-tip) : 7(S). The complex RN(SiMe_3)_2}(tmtu)Fe_4S_3]_2(μ_6-S){μ-N(SiMe_3)}_2 (1), obtained therefrom, consists of irons with a 6Fe(II)+2Fe(III) oxidation state, while PN consists of 8 Fe(II) ions. We have also isolated yet another type of [8Fe-7S] clusters, RSDmp)Fe4S312(μ_6-S)(μ-SDmP)_2 (μ-STip)} (2) (major) and [(STip)Fe_4S_3]_2(μ_6-S)(μ-SDmP)_2{μ-N(SiMe3)} (3) (minor), from the reaction of Fe{N(SiMe_3)_2}_2, HSDmp, HSTip, and elemental sulfur (8 : 6 : 10 : 7), which are topologically analogous to FeMo-co and have an intriguing 5Fe(II)+3Fe(III) oxidation state with a doublet ground state. Cluster 2 was also generated in 34% yield from the reaction of the di-iron complex [Fe(Stip)]_2(μ-SDmp)_2 with Sg.3. Dinuclear Fe-Ni complexes modelling the active site of [Ni-Fe] Hydrogenase : A tetranuclear Fe2Ni_2 complex, [(CO)_3Fe(μ-S^tBu)_3NiBr]_2, obtained from the reaction of FeBr_2(CO)_4, NaS^tBu, and NiBr_2(EtOH)_4 at 40℃, was found to serve as a convenient entry into a series of dinuclear Fe(CO)_3-Ni complexes. They include (CO)_3Fe(μ-S^tBu)_3NiBr(S=C(NMe_2)_2), [(CO)_3Fe(S^tBu)(R-S^tBu)_2Ni{S_2(C_6H_4)}], (CO)_3Fe(S^tBu) (R-S^tBu)_2Ni{S(CH_2)_2SMe}, (CO)_3Fe(μ-S^Bu)_3Ni(MeOH)(ortho-OC6_H4_SMe) (4), (CO)_3Fe(S^TBu)(μ-S^tBu)_2Ni (ortho-OC_6H_4SMe) (5), (CO)_3Fe(μ-S`tBu)_3Ni(THF)(OAc), (CO)_3Fe(μ-S`tBu)_3Ni(SDmp), and (CO)_3Fe (S`tBu)(μ-S`tBu)_2Ni(SDmp)(CO). Furthermore, we isolated (PPh_4)[(CO)_2(CN)_2Fe(μ-pdt)Ni(S_2CNR_2) (7) from the reaction of (PPh_4)[Fe(CO)_2(CN)_2(pdt)K] (6) with (PPh_3)NiBr(S_2CNR_2), which is the best structural model of [NiFe] hydrogenase reported so far. Less

1.硫醇盐/硫醚杂化配体对铁离子和镍离子的合理组装硫醇盐-硫在过渡金属原子上强烈配位，而硫醚型硫形成弱的M-S键，通常表现出容易的缔合/解离平衡。我们利用硫醇盐/硫醚杂化配体RSCH_2CH_2S(-) (R=Et (etet), R=^iPr (ptet), R=Ph (ptet))来组装铁(II)和Ni(II)金属离子。例如，NiCl_2 与 2 当量的 Li(etet) 反应生成线性聚合物 [Ni(etet)_2]n，而类似的 1:2 NiCl_/Li(ptet) 反应导致形成环状六核 [Ni_6(ptet)_<12>]。在这些介观尺寸的簇/聚合物中，硫醇盐-硫原子桥接Ni中心，使得硫醚硫不配位。当 NaSCH_2CH_2SR (R=Me (mtet)、R=Et (etet) 或 R=^iPr (^iptet)) 和 NaS^tBu 的 1:1 混合物用 1 当量的 NiCl_2 处理时，形成不寻常的环状十核簇 [Ni(SCH_2CH_2SR)(S^tBu)_<10>，其中溶剂… 更多的苯/THF分子被掺入到R=Et，^iPr.2的环空腔中。实现更好的铁硫簇建模固氮酶活性位点：P簇还原形式 (P^N) 的不寻常 [8Fe-7S] 无机核心结构是通过 Fe{N(SiMe_3)_2}_2, 四甲基硫脲 (tmtu), 2, 4, 的反应自组装的 6-三异丙基苯硫醇(HS-tip)和元素硫的比例为8(Fe):3(tmtu):12(HS-tip):7(S)。由此获得的配合物RN(SiMe_3)_2}(tmtu)Fe_4S_3]_2(μ_6-S){μ-N(SiMe_3)}_2 (1)由具有6Fe(II)+2Fe(III)氧化态的铁组成，而PN由8个Fe(II)离子组成。我们还分离出另一种类型的 [8Fe-7S] 团簇，RSDmp)Fe4S312(μ_6-S)(μ-SDmP)_2 (μ-STip)} (2)（主要）和 [(STip)Fe_4S_3]_2(μ_6-S)(μ-SDmP)_2{μ-N(SiMe3)} (3)（次要）， Fe{N(SiMe_3)_2}_2、HSDmp、HSTip 和元素硫 (8 : 6 : 10 : 7) 的反应，其拓扑类似于 FeMo-co，并具有有趣的 5Fe(II)+3Fe(III) 氧化态和双重态基态。双铁配合物 [Fe(Stip)]_2(μ-SDmp)_2 与 Sg.3 的反应也以 34% 的产率生成了簇 2。双核 Fe-Ni 配合物模拟 [Ni-Fe] 氢化酶的活性位点：四核 Fe2Ni_2 配合物 [(CO)_3Fe(μ-S^tBu)_3NiBr]_2 是由 FeBr_2(CO)_4、NaS^tBu 和 NiBr_2(EtOH)_4 在 40℃ 下反应获得的，被发现可以作为系列的便捷入口 双核 Fe(CO)_3-Ni 配合物。它们包括(CO)_3Fe(μ-S^tBu)_3NiBr(S=C(NMe_2)_2)、[(CO)_3Fe(S^tBu)(R-S^tBu)_2Ni{S_2(C_6H_4)}]、(CO)_3Fe(S^tBu) (R-S^tBu)_2Ni{S(CH_2)_2SMe}, (CO)_3Fe(μ-S^Bu)_3Ni(MeOH)(邻-OC6_H4_SMe) (4), (CO)_3Fe(S^TBu)(μ-S^tBu)_2Ni (邻-OC_6H_4SMe) (5)、(CO)_3Fe(μ-S`tBu)_3Ni(THF)(OAc)、(CO)_3Fe(μ-S`tBu)_3Ni(SDmp)和(CO)_3Fe(S`tBu)(μ-S`tBu)_2Ni(SDmp)(CO)。此外，我们从(PPh_4)[Fe(CO)_2(CN)_2(pdt)K] (6)与(PPh_3)NiBr(S_2CNR_2)的反应中分离出(PPh_4)[(CO)_2(CN)_2Fe(μ-pdt)Ni(S_2CNR_2) (7)，这是[NiFe]的最佳结构模型 目前已报道氢化酶。较少的

项目成果

R.Cao, K.Tatsumi: "Alkylation Reactions of [WS_4]^<2-> and [(η^5-C_5Me_5)WS_3]^-with 2,6-Bis(bromomethyl) pyridine : The First Isolation of Bis-alkylated Tetrathiometallate WS_2{2,6-(SCH_2)_2-(C_5H_3N)}"Inorg.Chem. 41(No.16). 4102-4104 (2002)

R.Cao、K.Tatsumi：“[WS_4]^<2-> 和 [(η^5-C_5Me_5)WS_3]^- 与 2,6-双(溴甲基)吡啶的烷基化反应：首次分离双-烷基化四硫代金属盐 WS_2{2,6-(SCH_2)_2-(C_5H_3N)}”Inorg.Chem.41(No.16).4102-4104(2002)

Coordination Chemistry of Silanedithiolato Ligands Derived from Cyclotrisilathiane : Synthesis and Structures of Complexes of Iron(II), Cobalt(II) Copper(I), and Silver(I).

环三硅硫烷衍生的硅烷二硫醇配体的配位化学：铁(II)、钴(II)、铜(I) 和银(I) 络合物的合成和结构。

• 发表时间: 2003
• 期刊: Inorg. Chem 42
• 作者: T.Komuro;T.Matsuo;H.Kawaguchi;K.Tatsumi
• 通讯作者: K.Tatsumi

Synthesis and Characterization of Ti(IV) and Ti(III) Complexes with (2-Dimethylphosphino) ethane-l-thiolate and (3-Dimethylphosphino)propane -1-thiolate as Ligands.

以（2-二甲基膦基）乙烷-1-硫醇盐和（3-二甲基膦基）丙烷-1-硫醇盐为配体的 Ti(IV) 和 Ti(III) 配合物的合成和表征。

• 发表时间: 2003
• 期刊: Inorg. Chem. 42
• 作者: K.Matsuzaki;H.Kawaguchi;P.Voth;K.Noda;S.Itoh;H.D.Takagi;K.Kashiwabara;K.Tatsumi
• 通讯作者: K.Tatsumi

T.Komuro, T.Matsuo, H.Kawaguchi, K.Tatsumi: "Copper ans Silver Complexes Containing a Novel S(SiMe_2S)_2^<2-> Ligand : Efficient Entries into Heterometallic Silfido Clusaters"Angew.Chem.Int.Ed. 41(No,1). 465-468 (2003)

T.Komuro、T.Matsuo、H.Kawaguchi、K.Tatsumi：“含有新型 S(SiMe_2S)_2^<2-> 配体的铜银配合物：有效进入异金属 Silfido 簇”Angew.Chem.Int.Ed

T.Komuro, T.Matsuo, H.Kawaguchi, K.Tatsumi: "Unusual Coordination Modes of Arylthiolates in Mo{η^5-SC_6H_3-2,6-(SiMe_3)_2} {η^7-SC_6H_3-2,6-(SiMe_3)_2"J.Am.Chem.Soc.. 125(No.8). 2070-2071 (2003)

T.Komuro、T.Matsuo、H.Kawaguchi、K.Tatsumi：“Mo{η^5-SC_6H_3-2,6-(SiMe_3)_2} {η^7-SC_6H_3-2,6 中芳基硫醇盐的异常配位模式-(SiMe_3)_2"J.Am.Chem.Soc..125(No.8)。2070-2071 (2003)