Rational Synthesis of Dynamic Complexes of Mezzoscopic-size

介观尺寸动态配合物的合理合成

基本信息

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

项目摘要

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。 /硫醚杂化配体RSCH_2CH_2S(-) (R=Et (etet), R=^iPr (ptet), R=Ph (ptet)) 组装铁(II) 和 Ni(II) 金属离子例如，NiCl_2 与 2 当量的 Li(etet) 反应产生 a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，当NaSCH_2CH_2SR (R=Me(mtet)，R)的1:1混合物时，硫醇盐-硫原子桥接Ni中心，使得硫醚硫不配位。 =Et (etet), 或 R=^iPr (^iptet)) 和 NaS^tBu 处理1当量的NiCl_2，形成了不寻常的环状十核簇[Ni(SCH_2CH_2SR)(S^tBu)_<10>，其中溶剂……更多苯/THF分子被纳入R=Et的环空腔中， ^iPr.2. 更好地模拟固氮酶活性位点：不寻常的 [8Fe-7S] 无机核通过Fe{N(SiMe_3)_2}_2、四甲基硫脲(tmtu)、2,4,6-三异丙基苯硫醇(HS-tip)反应自组装P簇(P^N)的还原型结构)，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，我们还分离出了另一种类型的 [8Fe-7S] 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），来自 Fe{N(SiMe_3)_2}_2、HSDmp、HSTip 和的反应元素硫 (8 : 6 : 10 : 7) 的拓扑类似于 FeMo-co，具有有趣的 5Fe(II)+3Fe(III) 氧化态和双峰簇 2，产率也为 34%。来自双铁配合物 [Fe(Stip)]_2(μ-SDmp)_2 与双核 Fe-Ni 配合物建模的反应。 [Ni-Fe]氢化酶的活性位点：四核Fe2Ni_2复合物，[(CO)_3Fe(μ-S^tBu)_3NiBr]_2，由FeBr_2(CO)_4、NaS^tBu和NiBr_2反应获得( EtOH)_4 在 40℃ 下被发现可以作为一系列双核 Fe(CO)_3-Ni 配合物的便捷入口。 (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，我们还分离出了 (PPh_4)[( CO)_2(CN)_2Fe(μ-pdt)Ni(S_2CNR_2) (7) 的反应(PPh_4)[Fe(CO)_2(CN)_2(pdt)K](6)与(PPh_3)NiBr(S_2CNR_2)，是目前报道的[NiFe]氢化酶最好的结构模型。