1995 Fiscal Year Final Research Report Summary
Synthesis of New Transition Metal Carbene Complexes Using the Caracteristics of Hypervalent Sulfur and Its applications
| Project/Area Number |
06640696
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Organic chemistry
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| Research Institution | University of Osaka Prefecture |
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Principal Investigator |
MATSUMURA Noboru University of Osaka Prefecture, College of Engineering, research Associate, 工学部, 助手 (40125274)
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| Co-Investigator(Kenkyū-buntansha) |
INOUE Hiroo University of Osaka Prefecture, College of Engineering, Professor, 工学部, 教授 (10081316)
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| Project Period (FY) |
1994 – 1995
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| Keywords | 10-S-3 Tetraazapentalene derivatives / Hypervalent sulfur / Trithiadiazapentalene derivatives / Thiadiselenadiazapentalene derivatives / Transition Metal Carbene Complexes |
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| Research Abstract |
The reactions of pi-sulfurane compounds with low valence transition metal complexes were in investigated. The results obtained are summarized below.
1.10-S-3 Tetraazapentalene derivatives reacted with Pd (PPh_3)_4, Pt (PPh_3)_4, and RhCl (PPh_3)_3 to give the carbene complexes of the [N-M-S] and/or [S-M-S] types (M=Pd, Pt, Rh) , respectively, accompanying the formation of triphenyl phosphine sulfide in the same ammount as that of the carbene complexes.
2. The structure of carbene complexes was determined by X-ray analysis. The Pd atom of [S-Pd-S] type has a square planar-coordinated structure surrounded by two sulfur ligands, one phosphorus ligand, and one carbene ligand. The structure of carbene complex of [N-Pd-S] type was determined by comparison of its spectral data with those of the carbene complexes of [S-Pd-S] type. The structure of Pt (II) carbene complex was similar to the structure of Pd (II) carbene complex.
3. The [N-Pd-S] type-carbene complex is stable to air in solid state but unstable in organic solvents at room temperature. Namely, the [N-Pd-S] type-carbene complex was completely converted into [S-Pd-S] type-carbene complex in refluxed benzene.
4. The X-ray crystallographic analysis of Rh (III) carbene complex showed the following structural features. (i) The Rh atom is octahedrally coordinated. (ii) The six coordinated-sites are occupied by one chloro ligand, two trans phosphine ligands, and one tridentate ligand formed by release of hypervalent sulfur. (iii) The C (1)-Rh bond length is very similar to that of known Rh (III) carbene complexes. (iv) This carbene complex is stable under air atmosphere.
5. Trithia-and thiadiselena-diazapentalene derivatives also reacted with Pd (PPh_3) _4, Pt (PPh_3) _4, and RhCl (PPh_3) _3 to give the carbene complexes of [Y-M-Y] types (Y=S or Se, M=Pd, Pt, Rh) , respectively, together with S=PPh_3.
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