An ew linear tetraphosphine containing aP NP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized andu tilized to support as eries of Pd/Pt mixed metal tetranuclearc hains, [Pd 4Àn Pt n (m-racdpmppan) 2 (XylNC) 2 ](PF 6 ) 2 (XylNC = xylyl isocyanide; n = 0: Pd 4 (1), 1: PtPd 3 (2), 2: PtPd 2 Pt (3), 2: Pt 2 Pd 2 (4), 3: Pt 2 PdPt (5)), in whicht he number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformationsf rom 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31 P{ 1 H} NMR and ESI mass spectra and X-ray diffractiona nalyses revealed almosti dentical tetranuclear structures, with slight contraction of metalmetal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1-5 exhibited characteristic bands at 635-510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (ds*ss*) to LUMO (ds*s*s*) transition by theoretical calculations.T he present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyedm etal chains by atomically precise Pt incorporation in the Pd 4 chain.[a] Prof.

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)-or (S,S)-dpmppm(=O) 4 , was synthesized to prepare C 2 dinuclear M(hfa) 3 complexes (M = Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa) 3 complexes (M = Eu, Y) with a P-chiral diphosphine dioxide,

Alloyed metal chains: A new linearly ordered tetraphosphine containing a PN(Ph)P phosphazane bridge, rac‐bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac‐dpmppan), was synthesized and utilized to scaffold a series of Pd4−nPtn mixed‐metal linear complexes [Pd4−nPtn(μ‐rac‐dpmppan)2(XylNC)2](PF6)2 (n=1—3), including Pd4, PtPd3, PtPd2Pt, Pt2Pd2, and Pt2PdPt chains, which are recognized as unprecedented alloyed metal atom chains. More information can be found in the Communication by T. Tanase, T. Nakajima et al. on page 8219.