| | 1 | Author
| Z. Naturforsch | Requires cookie* | | | Title
| Synthesis of Cationic Ruthenium Thioketene Complexes through Intramolecular 1,2-Elimination [1]  | | | | Abstract
| Halfsandwich thiocarboxylate complexes [CpRu(PR3)->(SC(0)CH2R')] ((P R 3)2 = (PPh3)2, Ph2PCH 2PPh2 (dppm), Ph2PC2H4PPh2 (dppe); R' = C6H 5, 4-C6H4Me, 4-C6H 4OMe, 4-C6H4C1) are obtained from the corresponding thiolate complexes [CpRu(PR3)2SH] and acyl chlorides. The structure of [CpRu(dppm)(SC(0)CHTPh)] was determined: monoclinic space group P2j/c (No. 14), a = 9.229(2), b = 16.680(3),"c = 21.447(5)Ä, ß = 90.751(12)°, Z = 4. Reaction of the thiocarboxylate complexes with the anhydrides of either trifluoro-acetic acid or trifluoromethanesulfonic acid gives thioketene complexes [CpRu(dppm) (?;2-S=C=CHR')]PF(s. H ie structure of [CpRu(dppm)0/2-S= C = C H Ph)]PF6 was deter mined: monoclinic space group P2,/c (No. 14), a -13.814(5), b -15.338(2), c = 17.057(7) Ä, ß = 93.74(2)°, Z = 4. | | | |
Reference
| (Z. Naturforsch. 52b, 117—124 [1997]; received July 25 1996) | | | |
Published
| 1997 | | | |
Keywords
| Ruthenium Complexes, Thiocarboxylate, Thioketene, Structure | | | |
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| default:Reihe_B/52/ZNB-1997-52b-0117.pdf | | | | Identifier
| ZNB-1997-52b-0117 | | | | Volume
| 52 | |
| 2 | Author
| WolfdieterA. Schenk, Bernhard Steinmetz3, Michael Hagel3, Waldemar Adamb, ChantuR. Saha-Möllerb | Requires cookie* | | | Title
| Oxyfunctionalization of Allyl Thioether Ruthenium Complexes with Dimethyldioxirane [1] | | | | Abstract
| Allyl thioether complexes [CpRu(P-P)(SRR')lPF6 (P-P = Ph2PCH2PPh2 (dppm), PIitPCtH-iPPI^ (dppe), R = Me, Et, Ph, R' = 3-propenyl, 3-cyclohexenyl, 2-methyl-2-buten-4-yl) and [CpRu(chir)(SRR')]PF6 (chir = (S,S)-Ph2PCHMeCHMePPh2, R = Me, CH2Ph, R' = 2-methyl-2-buten-4-yl) are obtained from the corresponding thiolate complexes by reaction with the appropriate allyl bromide. Careful oxidation with dimethyldioxirane (DMD) gave the allyl sulfoxide complexes [CpRu(P-P)(MeS(0)CH2CH=CH2)]PF6 (P-P = dppm, dppe). Double ox idation to the corresponding sulfinylmethyl epoxide complexes can be readily achieved with an excess of DMD. Oxidation of the chir complexes proceeds with only moderate diastereoselectiv-ity. The structure of the (/?, R/S, S) diastereomer of [CpRu(dppm)(MeS(0)CH2CHCH2 0)]PF6 was determined: monoclinic space group P2]/c (No. 14), a = 11.21(2), b = 16.762(9), c = 18.45(4) A, ß = 94.4(1)°, Z = 4. For a representative example, the decomplexation of the sulfoxide-epoxide ligand by sodium iodide in acetone was demonstrated. | | | |
Reference
| Z. Naturforsch. 52b, 1359—1371 (1997); received September 9 1997 | | | |
Published
| 1997 | | | |
Keywords
| Ruthenium Complexes, Sulfoxide, Epoxide, Dimethyldioxirane, Structure | | | |
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| default:Reihe_B/52/ZNB-1997-52b-1359.pdf | | | | Identifier
| ZNB-1997-52b-1359 | | | | Volume
| 52 | |
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