Synthesis and Catalytic Properties of Stimuli-Responsive Transition Metal Complexes Bearing Low-Coordinate Phosphorus Ligands

2016 Fiscal Year Final Research Report

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 24109010
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: Ozawa Fumiyuki 京都大学, 化学研究所, 教授 (40134837)
• Co-Investigator(Renkei-kenkyūsha): NAKAJIMA Yumiko 京都大学, 化学研究所, 助教 (80462711)
• Project Period (FY): 2012-06-28 – 2017-03-31
• Keywords: 感応性金属錯体 / 低配位リン化合物 / 配位子制御 / 結合活性化 / 触媒機能

Outline of Final Research Achievements

Phosphaalkenes with a P=C double bond possesses an extremely low-lying π* orbital, thereby serving as strong π-acceptors towards transition metals. We have found that this particular ligand property is useful in organometallic chemistry, leading to the following results. (1) PNP-pincer type phosphaalkene ligands effectively stabilize coordinatively unsaturated complexes of iron, nickel, and copper in low oxidation states. (2) A bis(phosphaethenyl)pyridine ligand forms very unusual platinum(0) complexes with a square planar configuration. (3) Noninnocent PNP-pincer type phosphaalkene complexes of iridium(I) rapidly cleave the N-H of ammonia and the C-H bond of acetonitrile at room temperature via metal-ligand cooperation. (4) The same iridium(I) complexes effectively catalyze hydrosilylation of carbon dioxide at room temperature under normal pressure.

Free Research Field

有機金属化学