Hg(II) sensing properties of (diphosphine)Pt(dmit) complexes (dmit: C3S52-: 1,3-dithiole-2-thione-4,5-dithiolate)

作者：Jeon Hyokyung; Suh Wooyoung; Noh Dong Youn^*

来源：Inorganic Chemistry Communications, 2012, 24: 181-185.

DOI：10.1016/j.inoche.2012.07.004

• Hg(II) ion sensing
• P2PtS2 core
• S center dot center dot center dot Hg(II) interaction
• Dithiolate ligand
• Diphosphine ligand

Heteroleptic chelate complexes with a [P2PtS2] core, (dppf)Pt(dmit) (1) and (dppe)Pt(dmit) (2), where dppf is 1,1'-bis(diphenylphosphino)ferrocene and dmit is 1,3-dithiole-2-thione-4.5-dithiolate, were shown to exhibit colorimetric sensing properties for the Hg(II) ion. The absorption peak for the pi -> pi* transition of the C=S moiety in the dmit ligand observed at 464 nm (epsilon = 1.2 x 10(4) M-1 cm(-1)) showed a bathochromic shift to 537 nm (epsilon = 0.8 x 10(4) M-1 cm(-1)) as [Hg(II)]/[1] was increased up to 300, which was accompanied by color change from yellow to purple. These changes resulted from the binding of Hg(II) ions to the C=S moiety. The affinity of (1) and (2) toward Hg(II) ion was estimated as K-d = 5.74 (+/- 0.40) x 10(-3) M for (1) and K-d = 5.60 (+/- 0.38) x 10(-3) M for (2). The metal- and dithiolate-substitutes of compound (1). (dPPf) Ni(dmit) (3) and (dppf)Pt(bdt) (4) where bdt is 1,2-benzenedithiolate, showed no Hg(II)-sensing ability due to the instability of (3) in solution and a lack of a Hg(II)-binding site for (4). The Hg(II)-sensing selectivity for (1) and (2) was also confirmed when compared to other metal ions, such as Cr(III), Fe(II), Co(II), Cu(II), Zn(II) and Ag(I).

• 出版日期2012-10