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  • 02월 19일 10시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제121회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Direct CO2 Addition to a Ni(0)-CO Species Allows the Selective Generation of a Nickel(II) Carboxylate with Expulsion of CO

2018년 3월 7일 09시 42분 04초
INOR.P-220 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
4월 19일 (목요일) 11:00~12:30
Inorganic Chemistry
저자 및
Dipankar Sahoo, Yunho Lee*
Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea

Pincer-type ligands are believed to be robust scaffolds that can support numerous functionalities as well as highly reactive metal motifs applied in organometallic chemistry. Carbon dioxide functionalization mediated by transition metal complexes has been widely explored in recent years to utilize CO2 as a synthetic C1 source. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO2 and its incorporation into synthetic organic molecules under mild conditions. Research in the field of catalytic reduction of carbon dioxide to a product such as formate, carbon monoxide, methanol or methane has grown rapidly in the past few decades. In order to exploit the insights from the biological CODH chemistry, we investigated the CO2 conversion chemistry at a single nickel center. Due to flexible nature of the PNP pincer ligand, the CO2 reaction of a nickel(0) species {Na}{(PNP)Ni(CO)} shows multiple product formation including a tetrameric cluster complex, which is a major problem of such ligand limiting its further applications. In order to block this undesired pathway, the PNP system was structurally rigidified to give the acriPNP ligand shows a planar structure with the small torsional angle between two aryl rings. A nickel(0)-CO complex with acriPNP ligand reveals selective CO2 addition to yield its nickel(II) carboxylate species with the expulsion of CO. By the successful isolation of the key intermediates, such as (acriPNP)Ni-μ-CO2-Na, (acriPNP)Ni-COOH-κC and {(acriPNP)Ni(CO)}+,0,– with their full characterizations, we finally discuss a closed synthetic cycle for the CO2 reduction to CO at a single nickel center.

“Direct CO2 Addition to a Ni(0)-CO Species Allows the Selective Generation of a Nickel(II) Carboxylate with Expulsion of CO” Sahoo, D., Yoo, C. and Lee, Y. J. Am. Chem. Soc. 2018, 140, 2179-2185.