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Abstract
A new linear hexaphosphine, rac-cis,cis,trans-bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]phenylphosphino}methane (P6), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene-bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M6(μ-P6)2]X6 (X6 = (OTf)6, M = Au (1), Ag (2); X6 = Cl2(PF6)4, M = Au (3)). The hexaphosphine also supported a tetrasilver(I) complex [Ag4(μ-P6)2](OTf)4 (4), which was readily transformed by treatment with AgOTf into 3, revealing a drastic alternation of the two P6 arrangement. The hexagold(I) chains exhibited a considerably red-shifted absorption (∼410 nm) and emission (540-580 nm) to (1) [5dσ*→6pσ] and from (3) [5dσ*→6pσ] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks.
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