Partyka David V, Robilotto Thomas J, Zeller Matthias, Hunter Allen D, Gray Thomas G
Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106, USA.
Proc Natl Acad Sci U S A. 2008 Sep 23;105(38):14293-7. doi: 10.1073/pnas.0806520105. Epub 2008 Sep 9.
A silver- and Brönsted acid-free protocol for generating the (tricyclohexylphosphine)gold(I) cation from the corresponding azide complexes is disclosed. The gold(I) cations so liberated are trapped by complexation with octaethylporphyrin. The first structurally authenticated gold(I) porphyrin complex crystallizes with formula C(72)H(112)Au(2)F(12)N(4)P(2)Sb(2), space group C2/c, a = 21.388 (4), b = 19.679 (4), c = 19.231 (3) A; beta = 111.030 (3) degrees. Solution spectroscopic studies indicate that the di-gold complex fragments on dissolution in organic solvents. Approximate density-functional theory calculations find an electrostatic origin for the binding of two gold(I) centers to the unprotonated nitrogen atoms, despite greater orbital density on the porphyrin meso carbons.
公开了一种无银和无布朗斯特酸的方法，用于从相应的叠氮化物配合物生成（三环己基膦）金（I）阳离子。如此释放出的金（I）阳离子通过与八乙基卟啉络合而被捕获。首个经结构验证的金（I）卟啉配合物结晶，化学式为C(72)H(112)Au(2)F(12)N(4)P(2)Sb(2)，空间群为C2/c，a = 21.388 (4)，b = 19.679 (4)，c = 19.231 (3) Å；β = 111.030 (3) 度。溶液光谱研究表明，该二金配合物在溶解于有机溶剂时会发生分解。近似密度泛函理论计算发现，尽管卟啉中位碳原子上的轨道密度更大，但两个金（I）中心与未质子化氮原子的结合源于静电作用。
