$C_{60}$ -metal cluster complexes: synthesis, characterization and theoretical studies = $C_{60}$ -금속 클러스터 화합물의 합성, 특성화 및 이론계산 연구

Cited 0 time in webofscience Cited 0 time in scopus
  • Hit : 338
  • Download : 0
The studies involve the synthesis, characterization, and theoretical studies of metallofullerene compounds. Heating a mixture of $Ir_4(CO)_9(PPh_3)_3$ (II-1) and 2 equiv of $C_{60}$ in refluxing chlorobenzene (CB) affords a “butterfly” $tetrairidium-C_{60}$ complex $Ir_4(CO)_6{μ_3-κ^3-PPh_2(ο-C_6H_4)P(ο-C_6H_4)PPh(η^1-ο-C_6H_4)}(μ_3-η^2:η^2:η^2-C_{60})$ (II-3, 36%). Brief thermolysis of II-1 in refluxing CB gives a “butterfly” complex $Ir_4(CO)_8{μ-κ^2-PPh_2(ο-C_6H_4)PPh}{μ_3-PPh_2(η^1:η^2-ο-C_6H_4)}$ (II-2, 64%) that is both ortho-phosphorylated and ortho-metalated. Interestingly, reaction of II-2 with 2 equiv of $C_{60}$ in refluxing CB produces II-3 (41%) by $C_{60}$ -assisted ortho-phosphorylation, indicating that II-2 is the reaction intermediate for the final product II-3. Compounds II-2 and II-3 have been characterized by spectroscopic and microanalytical methods as well as by single crystal X-ray diffraction studies. Cyclic voltammetry (CV) has been used to examine the electrochemical properties of II-2, II-3, and a related known “butterfly” complex $Ir_4(CO)_6(μ-CO){μ_3-κ^2-PPh_2(o-C_6H_4)P(η^1-o-C_6H_4)}(μ_3-η^2:η^2:η^2-C_{60})$ (II-4). These CV data suggest that a C60-mediated electron transfer to the iridium cluster center takes place for the species $II-3^{3-}$ and $II-4^{2-}$ in compounds II-3 and II-4. The electrochemical properties of II-3 and II-4 have been rationalized by molecular orbital calculations using the density functional theory (DFT) and by charge distribution studies employing the Mulliken and Hirshfeld population analyses. On the other hand, reaction of $Ir_4(CO)_8(PMe_3)_4$ (III-1) with excess (4 equiv) $C_{60}$ in refluxing 1,2-dichlorobenzene, followed by treatment with $CNCH_2Ph$ at $70^\circ C$, affords a square-planar complex with two $C_{60}$ ligands and a face-capping methylidyne ligand, $Ir_4(CO)_3(μ_4-CH)(PMe_3)_2(μ-PMe_2)(CNCH_2Ph)(μ-η^2:η^2-C_{60})(μ_4-η^1:η^1:η^2:η^2-C_{60})$ (III-2, 13%) as the major product. Compo...
Advisors
Park, Joon-Taikresearcher박준택researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2007
Identifier
263554/325007  / 020035113
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2007.2, [ viii, 97 p. ]

Keywords

Osmium; Iridium; Metal cluster; Rhenium; 레늄; 오스뮴; 이리듐; 금속 클러스터

URI
http://hdl.handle.net/10203/31677
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=263554&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
Files in This Item
There are no files associated with this item.

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0