Direct hydrosilylation by a zirconacycle with β-hydrogen
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Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.
For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.
The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
Azasilazirconacycle Cp2Zr{κ2-N(SiHMe2)SiHMeCH2} (1) and formaldehyde react through an uncatalyzed addition reaction (hydrosilylation) to form an exocyclic methoxysilyl-substituted zirconacycle. Although 1 contains 2-center-2-electron SiH groups, this transformation parallels the reactions of non-classical [Cp2ZrN(SiHMe2)2]+ ([2]+) with carbonyls. Reactions of 1 with a series of nucleophilic and electrophilic agents were explored, as well as reactions of related β-SiH-containing silazidozirconium compounds, to develop a rationale for the unexpected hydrosilylation. For example, carbon monoxide and 1 react at the Zr–C bond to form Cp2Zr{κ2-OC(CH2)SiHMeN(SiHMe2)} (7). The Lewis acid B(C6F5)3 also reacts at the Zr–C bond to give Cp2Zr{N(SiHMe2)SiHMeCH2B(C6F5)3} (8). OPEt3 and N,N-dimethylaminopyridine (DMAP) do not appear to interact with 1. In contrast, OPEt3 and DMAP react with non-classical compounds [2]+ and zwitterionic 8.
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This is a manuscript of an article published as Yan, KaKing, Aradhana Pindwal, Arkady Ellern, and Aaron D. Sadow. "Direct hydrosilylation by a zirconacycle with β-hydrogen." Dalton Transactions 43, no. 23 (2014): 8644-8653. DOI: 10.1039/C4DT00658E. Posted with permission.