Cyclic Trinuclear Rh_2M Complexes(M=Rh, Pt, Pd, Ni) Supported by meso-1, 3-Bis-{(diphenylphosphinomethyl) phenylphosphino} pr opane
Cyclic Trinuclear Rh_2M Complexes(M=Rh, Pt, Pd, Ni) Supported by meso-1, 3-Bis-{(diphenylphosphinomethyl) phenylphosphino} pr opane
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meso-1, 3-Bis-{(二苯基膦甲基)苯基膦}丙烷负载环状三核Rh_2M配合物(M=Rh, Pt, Pd, Ni)
DOI：
10.1021/om300278k
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发表时间：
2012
期刊：
影响因子：
2.8
通讯作者：
and T. Tanase
中科院分区：
文献类型：
--
作者：
T. Nakajima;S. Kurai;S. Noda;M. Zouda;B. Kure;and T. Tanase
[MCl2(cod)] （M = Pd, Pt）与四膦中位1,3-二[（二苯基膦甲基）苯基膦]丙烷（dpmppp）反应生成单核配合物[MCl2(dpmppp)] (M = Pd (3a), Pt (3b))，其中dpmppp配体通过两个内磷原子与M离子配位形成一个六元螯合环，两个外膦不配位。悬垂的外膦与[RhCl(CO)2]2反应生成阳离子杂核配合物[MRh2(μ-Cl)3(μ-dpmppp)(CO)2]X (X = [RhCl2(CO)2], M = Pd (4a), Pt (4b)；X = PF6, M = Pd （5a), Pt (5b)）。制备了镍类似物[NiRh2(μ-Cl)3(μ-dpmppp)(CO)2]PF6（5c）。由[RhCl(CO)2]2与dpmppp反应合成了中性三核Rh3配合物[Rh3(μ-Cl)3(μ-dpmppp)(CO)2](6)，再与HgX2（X = Cl, Br， I）反应得到Rh3Hg四核配合物[Rh3(HgX)(μ-Cl)2(μ-X)(μ-dpmppp)(CO)2]PF6(X = Cl(7a), Br (7b), I (7c))，其中Rh3(μ-Cl)2（μ-X）核作为三配体形成三个供体-受体Rh→Hg相互作用。7a - c的两个CO配体被XylNC取代，得到[Rh3(HgX)(μ-Cl)2(μ-X)(μ-dpmppp)(XylNC)2]PF6(X = Cl (8a), Br （8b), I (8c)）。异氰酸酯对三种Rh→Hg相互作用有明显的影响，这是通过31p {1H} NMR中观察到的2jhgpv值来监测的，并在DFT计算的基础上进行了讨论。络合物6还与CuCl和hbf4反应生成[Rh3(CuCl)(μ-Cl)3(μ-dpmppp)(CO)2](9)和[Rh3(μ - h)(μ-dpmppp)(CO)2]BF4（10）。这些结果表明，新的四膦dpmppm在构建可微调的异质金属框架方面是非常有用的。
Reaction of [MCl2(cod)] (M = Pd, Pt) with a tetraphosphine,meso-1,3-bis[(diphenylphosphinomethyl)phenylphosphino]propane (dpmppp), afforded the mononuclear complexes [MCl2(dpmppp)] (M = Pd (3a), Pt (3b)), in which the dpmppp ligand coordinated to the M ion by two inner phosphorus atoms to form a six-membered chelate ring with two outer phosphines uncoordinated. The pendant outer phosphines readily reacted with [RhCl(CO)2]2to give the cationic heterotrinuclear complexes [MRh2(μ-Cl)3(μ-dpmppp)(CO)2]X (X = [RhCl2(CO)2], M = Pd (4a), Pt (4b); X = PF6, M = Pd (5a), Pt (5b)). The nickel analogue [NiRh2(μ-Cl)3(μ-dpmppp)(CO)2]PF6(5c) was also prepared. A neutral homotrinuclear Rh3complex, [Rh3(μ-Cl)3(μ-dpmppp)(CO)2] (6), was synthesized by the reaction of [RhCl(CO)2]2with dpmppp and was further reacted with HgX2(X = Cl, Br, I) to afford the Rh3Hg tetranuclear complexes [Rh3(HgX)(μ-Cl)2(μ-X)(μ-dpmppp)(CO)2]PF6(X = Cl (7a), Br (7b), I (7c)), where the Rh3(μ-Cl)2(μ-X) cores act as tridentate ligands to form three donor–acceptor Rh→Hg interactions. The two CO ligands of7a–cwere replaced by XylNC to yield [Rh3(HgX)(μ-Cl)2(μ-X)(μ-dpmppp)(XylNC)2]PF6(X = Cl (8a), Br (8b), I (8c)). The isocyanides had an appreciable influence on the three Rh→Hg interactions, which was monitored by the2JHgPvalues observed in the31P{1H} NMR spectra and discussed on the basis of DFT calculations. Complex6also reacted with CuCl and HBF4to give [Rh3(CuCl)(μ-Cl)3(μ-dpmppp)(CO)2] (9) and [Rh3(μ3-H)(μ-Cl)3(μ-dpmppp)(CO)2]BF4(10), respectively. These results suggested that the new tetraphosphine dpmppm proved quite useful in constructing fine-tunable heterometallic frameworks.