Triosmium carbonyl complexes with multiple 1,3,5-triaza-7-phosphaadamantane (PTA) ligands: Synthesis of a new water-soluble Os₃ cluster

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• 作者：Amanda C. Dugan^a ; Brittney S.N. Nolan^a ; Kristen L. Brehm^a ; Joel L. Jackson Jr.^a ; Nigel Gwini^a ; Sarah D. Floris^a ; David M. Marolf^a ; James E. Johnstone^a ; Soo Hun Yoon^a ; Gregory L. Powell^a ; ^{powellg@acu.edu" class="auth_mail" title="E-mail the corresponding author} ; Vladimir N. Nesterov^b ; Hannah M. Johnston^c ; Kayla N. Green^c
• 关键词：Triosmium ; Carbonyl ; Cluster ; Water-soluble ; Phosphine
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：16 August 2016
• 年：2016
• 卷：114
• 期：Complete
• 页码：292-298
• 全文大小：851 K

文摘

Microwave heating has been used to substitute carbonyl ligands for 1,3,5-triaza-7-phosphaadamantane (PTA) ligands on the Os₃(CO)₁₂ molecule. Os₃(CO)₁₁(PTA) (1) has been prepared in 66% yield by the reaction of Os₃(CO)₁₂ with MeCN, followed by reaction with one mole equivalent of PTA. Os₃(CO)₁₀(PTA)₂ (2) has been prepared in 65% yield via a three-step reaction. First, Os₃(CO)₁₂ was heated in MeCN. Next, one mole equivalent of PTA was added to this reaction mixture. Finally, one mole equivalent of trimethylamine-N-oxide was added followed by another mole equivalent of PTA. Additionally, Os₃(CO)₉(PTA)₃ (3) has been prepared in 85% yield by the reaction of Os₃(CO)₁₂ with 3.5 mol equivalents of PTA in 1,2-dichlorobenzene, and Os₃(CO)₈(PTA)₄ (4) has been prepared in 36% yield by the reaction of Os₃(CO)₁₂ with 8 mol equivalents of PTA in a mixture of acetonitrile and 1,2-dichlorobenzene. The solubilities of clusters 1–4 in water at various pH levels have been studied, and 4 was found to be soluble in water with a neutral pH. X-ray diffraction has been used to determine the crystal structures of clusters 1 and 3. The X-ray crystal structure of a protonated form of 3, [Os₃(CO)₉(PTAH)₃]Cl₃ (5), has also been determined. All PTA ligands occupy equatorial coordination sites on the triangular Os₃ units.