Abstract
Reaction of AgOTf with a tetraphosphine, rac-bis[(diphenylphosphinomethyl) phenylphosphino]methane (rac-dpmppm), afforded [Ag4(rac-dpmppm)2](TfO)4 (3) which consists of zigzag-arrayed tetranuclear silver(I) ions supported by syn-arrangement of two enantiomeric (RR/SS) dpmppm ligands. Complex 3 readily reacted with XylNC (Xyl = 2,6-dimethylphenyl) to give [Ag4(rac-dpmppm)2(XylNC)2](TfO)4 (4), where two terminal isocyanides attach to the outer Ag sites. Complex 3 has been shown a good precursor for Pt-Ag-Ag-Pt mixed metal array as incubation of 3 with trans-[Pt(CCPh)2(PPh3)2] yielded [Ag2Pt2(CCPh)4(rac-dpmppm)2](TfO)2 (5). Two trans-Pt(CCPh)2 units are incorporated into the terminal positions in a site-selective fashion and the Pt-Ag-Ag-Pt tetranuclear core also adopts a zigzag array supported by syn-arrangement of two rac-dpmppm ligands. The d8 and d10 closed-shell mixed metal centers of 5 exhibited an intense photoluminescence at 534 nm, mainly from an unsymmetric triplet state generated by charge transfer transitions from ligand (acetylide π) to metal centers (Ag2 and PtAg s/pσ), 3LMCT, and to ligands (acetylide π* and dpmppm), 3LLCT. The present results provide fundamental and useful information to construct multinuclear closed-shell metal alignments by utilizing polyphosphine ligands.
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