Syntheses, Structural Determination, and Electrochemistry of Ru2(Fap)4Cl and Ru2(Fap)4(NO)Cl

详细信息    查看全文

• 作者：John L. Bear ; Julien Wellhoff ; Guy Royal ; Eric Van Caemelbecke ; Sonia Eapen ; and Karl M. Kadish
• 刊名：Inorganic Chemistry
• 出版年：2001
• 出版时间：May 7, 2001
• 年：2001
• 卷：40
• 期：10
• 页码：2282 - 2286
• 全文大小：80K
• 年卷期：v.40,no.10(May 7, 2001)
• ISSN：1520-510X

文摘

Ru₂(Fap)₄Cl and Ru₂(Fap)₄(NO)Cl, where Fap is the 2-(2-fluoroanilino)pyridinate anion, were synthesized, andtheir structural, electrochemical, and spectroscopic properties were characterized. Ru₂(Fap)₄Cl, which was obtainedby reaction between Ru₂(O₂CCH₃)₄Cl and molten HFap, crystallizes in the monoclinic space group P2₁/c, witha = 11.2365(4) Å, b = 19.9298(8) Å, c = 19.0368(7) Å, = 90.905(1), and Z = 4. The presence of threeunpaired electrons on the Ru₂⁵⁺ core and the 2.2862(3) Å Ru-Ru bond length for Ru₂(Fap)₄Cl are consistentwith the electronic configuration ()²()⁴()²(*)²(*)¹. The reaction between Ru₂(Fap)₄Cl and NO gas yieldsRu₂(Fap)₄(NO)Cl, which crystallizes in the orthorhombic space group Pbca, with a = 10.0468(6) Å, b = 18.8091(10) Å, c = 41.7615(23) Å, and Z = 8. The Ru-Ru bond length of Ru₂(Fap)₄(NO)Cl is 2.4203(8) Å, while itsN-O bond length and Ru-N-O bond angle are 1.164(8) Å and 155.8(6), respectively. Ru₂(Fap)₄(NO)Cl canbe formulated as a formal Ru₂^II,II(NO⁺) complex with a linear Ru-N-O group, and the proposed electronicconfiguration for this compound is ()²()⁴()²(*)³(*)¹. The binding of NO to Ru₂(Fap)₄Cl leads to somestructural changes of the Ru₂(Fap)₄ framework and a stabilization of the lower oxidation states of the dirutheniumunit. Also, IR spectroelectrochemical studies of Ru₂(Fap)₄(NO)Cl show that NO remains bound to the complexupon reduction and that the first reduction involves the addition of an electron on the diruthenium core and noton the NO axial ligand.