d-pi Interaction in Transition Metal Cluster Complexes and Their Properties
| Project/Area Number |
09650900
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | GIFU UNIVERSITY |
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Principal Investigator |
KAWAMURA Takashi Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (40026125)
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| Co-Investigator(Kenkyū-buntansha) |
EBIHARA Masahiro Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (80201961)
TSUJI Yasushi Hokkaido University, Center of Catalysis Research, Professor, 触媒化学研究センター, 教授 (30144330)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1998: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | cluster complex / ionic radical / magnetism / crystal structure / pi stack / rhodium / aromatic ligand / iridium / 金属原子間結合 / 電子非局在化 / ルテニウム / イオウ原子間相互作用 |
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| Research Abstract |
Transition metal cluster complexes of rhodium and iridium with aromatic or chloro bridging ligands have been prepared, their structure and physicochemical properties have been studied and following results have been obtained.
1. The reaction of dinuclear rhodium complexes with silyl chlorides gave new type of tetranuclear rhodium complexes with chloro-bridges.
2. The symmetry and delocalization of the singly occupied molecular orbitals (SOMO) of rhodium dinuclear complexes were shown to be heavily dependent on ligands based on X-ray structures and DFT theoretical calculations. A large mixing of
siguma_<RhRh> and n_p orbitals were observed for Rh_2^<5+> complexes with axial phosphine ligands. The pi_<RhRh>* orbital is localized on the metal atoms and the orbital is moderately delocalized onto the pi system of the bridging ligands.
3. Diiridium complexes with bridging aminopyridine ligands were shown to have low oxidation potentials and short metal-metal separations.
4. The delta* SOMO of Rh_2^<5+> complexes with hydroxypyridine ligands were shown to be delocalized onto the aromatic bridging ligands to the extent of about 10 %. In crystal, Rh_2^<4+> and Rh_2^<5+> complexes were packed with pi stacked arrangement of aromatic bridgeing ligands. Electric conductance of some of Rh_2^<5+> complexes were in the order of 10^<-7> S cm^<-1> (room temperature, pellets). Magnetism of crystals of Rh_2^<5+> complexes with aromatic bridging ligands were analyzed in relation to their crystal stucture.
5. Square planar Pd(II) and Pt(II) complexes with silyl or stannyl and phosphine ligands showed facile twist-rotational unimolecular isomerization.
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Report
(3 results)
Research Products
(9 results)
