Synthesis and Reactivity of Thiolate-Bridged NiIIMIHeterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2Metalloligand: Synthesis and Reactivity of Thiolate-Bridged NiIIMIHeterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2Metalloligand
Synthesis and Reactivity of Thiolate-Bridged NiIIMIHeterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2Metalloligand: Synthesis and Reactivity of Thiolate-Bridged NiIIMIHeterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2Metalloligand
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DOI：
10.1002/ejic.201700682
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发表时间：
2017-09
影响因子：
2.3
通讯作者：
B. Kure;M. Sano;Natsuki Watanabe;Takayuki Nakajima;T. Tanase
中科院分区：
文献类型：
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作者：
B. Kure;M. Sano;Natsuki Watanabe;Takayuki Nakajima;T. Tanase
单核配合物[Ni(meppp)] {H2meppp =meso-1,3-bis[(2-巯基乙基)(苯基)膦基]丙烷}作为S-二齿NiP2S2金属配体，制备了一系列具有各种中性配体的NiIIIMI配合物，即[Ni(μ-meppp)ML2]PF6[M = Rh, L = 1/2cod (1a; cod = 1,5-环辛二烯)、CO (1b)、XylNC (1c；Xyl = 2,6-二甲基苯基)、P(OPh)3(1d)； M = Ir，L = 1/2cod (2a)，CO (2b)，XylNC (2c)]。检测了1和2对碘甲烷和叔氢硅烷的反应性。络合物 1c、2a 和 2 与 MeI 反应生成氧化加成产物 [Ni(μ‐meppp)M(L)2(Me)(I)]PF6[M = Rh, L = XylNC (3c)； M = Ir，L = 1/2cod (4a)] 和 [Ni(μ‐meppp)Ir(CO)(Me)(I)2] (5)。在与氢硅烷的反应中，只有2c表现出有趣的反应性，形成NiII(μ-H)IrIII甲硅烷基络合物[Ni(μ-meppp)(μ-H)Ir(XylNC)2(Si)]PF6[Si= SiEt3(6a)、SiMe2Ph (6b)、SiMePh2(6c)、SiPh3(6d)]。反应通过中间异构体 [Ni(meppp)(μ-H)Ir(XylNC)2(Si)]PF6(7) 进行；中间体 7d(Si= SiPh3) 被表征为具有 NiII(μ-H)IrIII 甲硅烷基结构，氢配体嵌套在 Ni(μ-S)2Ir 口袋与 6d 口袋相反的一侧。这些结果表明，双（硫醇盐）桥联的 NiIIIMI 异双核配合物的反应活性可以通过改变金属离子和辅助配体来调节。此外，由于铰接的Ni(μ-SR)2Ir结构的灵活性，S-二齿NiP2S2金属配体[Ni(meppp)]在NiII(μ-H)IrIII核心两个口袋中桥联氢配体的稳定中发挥着重要作用。
The mononuclear complex [Ni(meppp)] {H2meppp =meso‐1,3‐bis[(2‐mercaptoethyl)(phenyl)phosphino]propane} was used as an S‐bidentate NiP2S2metalloligand to prepare a series of NiIIMIcomplexes with various neutral ligands, namely, [Ni(µ‐meppp)ML2]PF6[M = Rh, L = 1/2cod (1a; cod = 1,5‐cycloocatadiene), CO (1b), XylNC (1c; Xyl = 2,6‐dimethylphenyl), P(OPh)3(1d); M = Ir, L = 1/2cod (2a), CO (2b), XylNC (2c)]. The reactivities of1and2toward methyl iodide and tertiary hydrosilanes were examined. Complexes1c,2a, and2breacted with MeI to afford the oxidative addition products [Ni(µ‐meppp)M(L)2(Me)(I)]PF6[M = Rh, L = XylNC (3c); M = Ir, L = 1/2cod (4a)] and [Ni(µ‐meppp)Ir(CO)(Me)(I)2] (5). In the reactions with hydrosilanes, only2cexhibited an interesting reactivity to afford the NiII(µ‐H)IrIIIsilyl complexes [Ni(µ‐meppp)(µ‐H)Ir(XylNC)2(Si)]PF6[Si= SiEt3(6a), SiMe2Ph (6b), SiMePh2(6c), SiPh3(6d)]. The reaction proceeded via the intermediate isomers [Ni(meppp)(µ‐H)Ir(XylNC)2(Si)]PF6(7); intermediate7d(Si= SiPh3) was characterized and has an NiII(µ‐H)IrIIIsilyl structure with the hydrido ligand nesting in the reverse side of the Ni(µ‐S)2Ir pocket to that of6d. These results demonstrated that the reactivities of the bis(thiolate)‐bridged NiIIMIheterodinuclear complexes can be tuned by changing the metal ions and ancillary ligands. In addition, the S‐bidentate NiP2S2metalloligand [Ni(meppp)] plays an important role in the stabilization of the bridging hydrido ligand in both pockets of the NiII(µ‐H)IrIIIcore owing to the flexibility of the hinged Ni(µ‐SR)2Ir structure.