Photoreduction of Pt(IV) Chloro Complexes: Substrate Chlorination by a Triplet Excited State
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https://figshare.com/articles/dataset/Photoreduction_of_Pt_IV_Chloro_Complexes_Substrate_Chlorination_by_a_Triplet_Excited_State/2272702
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资源简介：
The
Pt(IV) complexes trans-Pt(PEt3)2(Cl)3(R) 2 (R = Cl, Ph, 9-phenanthryl,
2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-perylenyl) were
prepared by chlorination of the Pt(II) complexes trans-Pt(PEt3)2(R)(Cl) 1 with Cl2(g) or PhICl2. Mixed bromo–chloro complexes trans,trans-Pt(PEt3)2(Cl)2(Br)(R) (R = 9-phenanthryl, 4-trifluoromethylphenyl), trans,cis-Pt(PEt3)2(Cl)2(Br)(4-trifluoromethylphenyl), trans,trans-Pt(PEt3)2(Br)2(Cl)(R) (R
= 9-phenanthryl), and trans,cis-Pt(PEt3)2(Br)2(Cl)(4-trifluoromethylphenyl)
were obtained by halide exchange or by oxidative addition of Br2 to 1 or Cl2 to trans-Pt(PEt3)2(R)(Br). Except for 2 (R = Ph, 4-trifluoromethylphenyl), all of the Pt(IV) complexes are
photosensitive to UV light and undergo net halogen reductive elimination
to give Pt(II) products, trans-Pt(PEt3)2(R)(X) (X = Cl, Br). Chlorine trapping experiments
with alkenes indicate a reductive-elimination mechanism that does
not involve molecular chlorine and is sensitive to steric effects
at the Pt center. DFT calculations suggest a radical pathway involving 3LMCT excited states. Emission from a triplet is observed in
glassy 2-methyltetrahydrofuran at 77 K where photoreductive elimination
is markedly slowed.
创建时间：
2014-07-21
