Synthesis and Reactivity of Thiolate-bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) Using a S-Bidentate NiP2S2 Metalloligand
Synthesis and Reactivity of Thiolate-bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) Using a S-Bidentate NiP2S2 Metalloligand
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使用 S-二齿 NiP2S2 金属配体合成硫醇盐桥联 NiIIIMI 异双核配合物 (M = Rh, Ir) 及其反应活性
DOI：
10.1002/ejic.201700937
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发表时间：
2017
影响因子：
2.3
通讯作者：
Tomoaki*
中科院分区：
文献类型：
--
作者：
Kure;Bunsho;* Sano;Mikie; Watanabe;Natsuki; Nakajima;Takayuki; Tanase;Tomoaki*
单核配合物[Ni（meppp）] {H2 meppp =meso-1，3-bis[以[2-巯基乙基]（苯基）膦基]丙烷}为S-双齿NiP_2S_2配体，合成了一系列与中性配体的NiIIMI配合物[Ni（μ-meppp）ML_2] PF_6 [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）]。考察了1和2与碘甲烷和叔氢硅烷的反应活性。配合物1c、2a和2与MeI反应，得到氧化加成产物[Ni（μ-meppp）M（L）2（Me）（I）] PF 6 [M = Rh，L = XylNC（3c）; M = Ir，L = 1/2cod（4a）]和[Ni（μ-meppp）Ir（CO）（Me）（I）2]（5）。在与氢化硅烷的反应中，只有2c表现出有趣的反应性，得到Ni II（μ-H）Ir III硅基配合物[Ni（μ-meppp）（μ-H）Ir（XylNC）2（Si）] PF 6 [Si= SiEt 3（6a），SiMe 2 Ph（6 b），SiMePh 2（6c），SiPh 3（6d）]。该反应通过中间体异构体[Ni（meppp）（µ-H）Ir（XylNC）2（Si）] PF 6（7）进行;中间体7 d（Si= SiPh 3）被表征，具有NiII（µ-H）Ir III甲硅烷基结构，其中配位体嵌套在Ni（µ-S）2 Ir口袋的反面，与6d相反。这些结果表明，通过改变金属离子和辅助配体，可以调节双硫醇桥联NiIIMI异双核配合物的反应活性.此外，S-双齿NiP 2S 2金属配体[Ni（meppp）]由于铰链Ni（µ-SR）2 Ir结构的灵活性，在NiII（µ-H）IrIIIcore的两个口袋中的桥连配体的稳定中起着重要作用。
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.