2019 Fiscal Year Research-status Report
Binuclear Sandwiches of the Main Group Elements
| Project/Area Number |
18K05137
|
|---|
| Research Institution | University of Tsukuba |
|---|
Principal Investigator |
Lee Vladimir 筑波大学, 数理物質系, 講師 (90375410)
|
|---|
| Project Period (FY) |
2018-04-01 – 2021-03-31
|
| Keywords | cluster / group 15 element / binuclear sandwich / pyramidane / bis(housene) / cyclobutadiene dianion / NMR spectroscopy / X-ray crystallography |
|---|
| Outline of Annual Research Achievements |
The goal of the current project is the study of a novel class of the highly strained polyhedral clusters, pyramidanes and isomeric housenes. very interesting because of their unusual structures and bonding natures. They are also promising as precursors for novel type of polymers, ceramics and nanoobjects in material science. In accord with the initially proposed plan, during the second year of the project, we successfully synthesized first representatiave of bis(housenes) with antimony as the central elements. Moreover, cationic monopyramidanes with the apical heavier group 15 elements were also synthesized, isolated and structurally characterized. We also optimized the reaction conditions to maximize the yields of target products.
|
| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
During the second year of the project, our original plan was successfully realized and initially planned synthetic goals were fully achieved.
Thus, the target bis(housene) [(Me3Si)4C4]E-E[C4(SiMe3)4] (E = Sb) was successfully prepared and fully structurally characterized, its unique bonding situation was computationally studied. In addition, we synthesized novel cationic pyramidanes with the heavier group 15 elements at the top of the square-pyramid. For preparation of the target bis(pyramidanes), we performed a detailed computational study to suggest synthetic strategies for their experimental realization. Thus, we can conclude that during its second year, our project was progressing rather smoothly without any troubles, in accord with the originally proposed research plan and schedule.
|
| Strategy for Future Research Activity |
For the following third year of the project, we will attempt synthesis of the bis(pyramidanes), as the binuclear sandwiches of the main group elements, by the reductive dehalogenation of the previously synthesized mono(halo)pyramidane precursors with alkali or alkaline-earth metals. Next, we will attempt synthesis of the most challenging poly(pyramidanes) and poly(housenes), starting from bis(pyramidanes) and bis(housenes) or from mono(pyramidanes) and mono(housenes). Structures, reactivity and potential applications of all novel clusters will be also comprehensively studied both experimentally (X-ray, NMR) and computationally (AIM, ELF). Particular attention will be paid to the systematic study of the influence of substituents and skeletal atoms on the stability of polyhedral systems.
|
| Causes of Carryover |
For the second year of the project, the originally required amount (including amount unused from previous fiscal year and indirect costs) was 1,440,696 yen (B), but actually 1,352,989 yen (A) were used. Such difference is caused by change in our original plan to purchase some chemical reagents, because it was possible to carry out our experiments without such reagents to achieve the research goals. Money remaining after the second year of the project, 87,707 yen (B-A), are transferred to the third year of the project, and will be used to purchase necessary chemical reagents.
|
-
-
-
-
-
-
-
-
-
-
-
[Presentation] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019
Author(s)
Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
Organizer
8th JACI/GSC Symposium 2019(Japan Association for Chemical Innovation/Green and Sustainable Chemistry), Tokyo, Tokyo International Forum, 24-25 June
-
[Presentation] Catalytic Performance of Novel Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019
Author(s)
Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, K. Matsumoto, J.-C. Choi, N. Fukaya
Organizer
66th Symposium on Organometallic Chemistry, Tokyo, Tokyo Metropolitan University, 14-16 September
-
[Presentation] Catalytic Performance of Silyl Group-Substituted N-Heterocyclic Carbene Complexes2019
Author(s)
Y. Seo, T. Mizusaki, Y. Takagi, K. Hatakeyama, V. Ya. Lee, Y.-K. Choe, K. Matsumoto, J.-C. Choi, N. Fukaya
Organizer
100th Annual Meeting of The Chemical Society of Japan, Noda, Tokyo University of Science, 22-25 March
-
