2003 Fiscal Year Final Research Report Summary
Syntheses of Cluster Complexes with high nuclearity based on metal to metal dative bonds
| Project/Area Number |
14540508
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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 |
Inorganic chemistry
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| Research Institution | Tohoku University |
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Principal Investigator |
YAAMGUCHI Tadashi Tohoku Univ., Graduate school of Science, Associate Professor, 大学院・理学研究科, 助教授 (40230362)
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| Project Period (FY) |
2002 – 2003
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| Keywords | metal-metal dative bond / platinum complexes / cluster complexes |
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| Research Abstract |
It has been shown that the occupied d_<z^2> orbital of a d^8 metal ion with square-planar coordination geometry can act as a potential donor to another metal ion (M) resulting in a dative M(d^8) to M bond. In this study we aim to synthesize cluster complexes with high nuclearity based on short unsupported Pt(II) to M dative bonds.
1.When the rhodium dimer [Rh_2(CF_3COO)_4] was used as an acceptor, heterometal tetranuclear cluster core was obtained. In the case of using of [Pt(phpy)_2], [Pt(bpy)Me_2] as a donor, the tetranuclear Pt→Rh_2→Pt complexes, [{Rh_2(CF_3COO)_4} {Pt(phpy)_2}_2], [{Rh_2(CF_3COO)_4} {Pt(bpy)Me_2}_2] was obtained in which the platinum complexes coordinate to axial sites of rhodium dimer. In contrast, use of [Pt(thpy)_2] results in formation of linear chain compounds in which Pt_2Rh_2tetranuclear core similar to the above clusters, and rhodium dimer are connected by S-Rh bond. The cluster has both platinum to silver dative bonds and a rhodium-rhodium single bond.
2.From a reaction of biphenyl derivative, [Pt(dbbp)(L)] (H_2dbbp = di-tert-butylbiphenyl, L = 2,2 -bipyridine or ethylenediamine) and silver ion, rhombus Pt_2Ag_2 cluster complexes was obtained even though less coordinative counter anion is used. These results are in contrast with the case of using [Pt(phpy)_2], [Pt(thpy)_2] as a donor, in which linear chain compounds are obtained when less coordinative counter anion is used.
These results show not only that platinum complexes in a strong ligand field can make a strong platinum to metal dative bond, but also that the metal-metal dative bond is useful for making large cluster complexes.
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