Tetranuclear Pd4, PtnPd4-n (n = 1-3), and Pt4 Chains Supported by rac- and meso-Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2 Tuned by Changing N-Substituents, P-Configuration, and Terminal Ligands
Tetranuclear Pd4, PtnPd4-n (n = 1-3), and Pt4 Chains Supported by rac- and meso-Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2 Tuned by Changing N-Substituents, P-Configuration, and Terminal Ligands
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由外消旋和内消旋 Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2 支持的四核 Pd4、PtnPd4-n (n = 1-3) 和 Pt4 链，通过改变 N 取代基、P 构型和末端进行调整
DOI：
10.1002/ejic.202200248
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
T. Nakajima
中科院分区：
文献类型：
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作者：
T. Tanase;Y. Fujisawa;Y. Morita;Y. Ura;T. Nakajima
With the hope of tuning structural and electronic properties of the metal chains by changing theN‐substituent group andP‐chiral configurations, a series of PNP bridged tetraphosphines,rac‐ andmeso‐Ph2PCH2P(Ph)N(Ar)P(Ph)CH2PPh2(Ar=4‐RC6H4, R=F (rac‐dpmppanF), CH3(rac‐dpmppanMe), H (meso‐dpmppan), OMe (meso‐dpmppanOMe); Ar=2,4‐xylyl (rac‐dpmppanMe2)), were synthesized, and utilized to prepare the Pd4and Pt2Pd2chains with XylNC terminal ligands, [M4(rac‐dpmppanR)2(XylNC)2](PF6)2(M4=Pd4,R=F (1F), Me (1Me); M4=Pt2Pd2,R=F (4F), Me (4Me)) and [M4(meso‐dpmppanR)2(XylNC)2](PF6)2(M4=Pd4,R=H (6), OMe (6OMe); M4=PdPt2Pd,R=OMe (9OMe)). While the M4metal chains withrac‐dpmppanR(R=H, F, Me) ligands showed only marginal effects on the tetranuclear metal chains, themesostereoisomer ofmeso‐dpmppanOMe afforded a new series of Pd4(6OMe), PtPd3(7OMe), PtPd2Pt (8OMe), PdPt2Pd (9OMe), Pt3Pd (10OMe), and Pt4(11OMe) chains that exhibited a characteristic electronic absorption band tunable by the number and positions of incorporated Pt atoms from 628 nm to 473 nm. Especially,11OMeis the first example of Pt4chains supported by tetraphosphines. The coordinatively unsaturated Pd4strings, [Pd4(rac‐dpmppan)2(CH3CN)](BF4)2(12) and [Pd4(meso‐dpmppanOMe)2](BF4)2(13), were also synthesized and12was utilized in axial ligand exchange reactions with PPh2Me, and PPh3to disclose their successive incorporation into [Pd4(rac‐dpmppan)2(L)2](BF4)2(L=PPh2Me (14 a), PPh3(14 b)) and remarkable red‐shift (713–718 nm) of the HOMO‐LUMO transition of the Pd4chains. The linear Pd4, PtnPd4‐n(n=1–3), and Pt4complexes obtained in the present study could be useful 1D building blocks for assembling through metal−metal interaction.
