| Project/Area Number |
24550038
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | University of Tsukuba |
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Principal Investigator |
LEE Vladimir 筑波大学, 数理物質系, 講師 (90375410)
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| Project Period (FY) |
2012-04-01 – 2015-03-31
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| Project Status |
Completed (Fiscal Year 2014)
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| Budget Amount *help |
¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2014: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2012: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
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| Keywords | cycloaddition / germylene / metathesis / Schrock complex / silylene / Schrock-type complexes / early transition metals / [2+2] cycloaddition / bicyclo[1.1.0]butane / metallacyclobutane / heavy Group 14 elements / Main Group Element / Transition Metal / Schrock-type Complex / Lewis Base Ligand / Titanium / Silylidene / Double Bond / Bond Polarization |
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| Outline of Final Research Achievements |
Metathesis of unsaturated hydrocarbons is among the most technologically useful alkene transformations. The Si and Ge variations of the metathesis represent a new promising route for the synthesis of the highly reactive multiply-bonded organosilicon and organogermanium compounds as precursors for the advanced materials of the new generation. In this project we developed the first examples of the Schrock-type alkylidene complexes of Si and Ge, namely, silylidenes and germylidenes, of the early transition metals. Thus, stable silylene and germylene complexes of the group 4 metals were prepared, isolated, structurally characterized, and computationally studied. All data support classification of such complexes as Schrock-type silylidenes and germylidenes, which react with unsaturated substrates (alkynes, alkenes, nitriles) forming the corresponding [2 + 2] cycloadducts, whose particular structures and cycloreversion were studied both experimentally and computationally.
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