Dinuclear Rhodium Complexes Containing the Diyne 1,4-C6H4(C≡CH)2 and the Isomeric Bisvinylidene 1,4-C6H4(CH=C:)2 as Bridging Units |
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Authors: | Helmut Werner Thomas Rappert Justin Wolf |
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Affiliation: | Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-8700 Würzburg, FRG |
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Abstract: | The reaction of RhCl(PiPr3)2] ( 1 ) with 1,4-C6H4(C≡CH)2 at 0°C leads almost quantitatively to the formation of the bis(alkyne) complex (PiPr3)2ClRh-(HC≡C6H4-C≡CH)RhCl(PiPr3)2] (2). At elevated temperatures (THF, 60°C) it rearranges to give the isomeric bis(vinylidene) complex (PiPr3)2ClRh-(=C=CH-C6H4-CH=C=)RhCl(PiPr3)2] (3). A one-pot synthesis of 3 is also described. Treatment of either 2 or 3 with pyridine affords the bis(alkynyl)dihydrido compound (PiPr3)2(py)Cl(H)Rh(-C≡C-C6H4-C≡C-)Rh(H)Cl(py)(PiPr3)2] ( 4 ) in which both metal centers are octahedrally coordinated. Whereas the reaction of 2 with NaC5H5 produces the complex CsH5(PiPr3)Rh(HC≡C-C6H4-C≡CH)Rh(PiPr3)C5H5 ( 7 ), the bis(vinyl-idene) isomer C5H5(PiPr3)Rh(=C=CH-C6H4-CH=C=)Rh(PiPr3)C5Hs ( 8 ) is obtained from 4 and NaC5H5. Electrophiles preferably attack the Rh=C bonds of 8 and thus on protonation with CF3CO2H the bis(vinyl) complex C5H5(PiPr3)(CF3CO2)-Rh(Z,Z-CH=CH-C6H4-CH=CH)Rh(O2CCF3)(PiPr3)C5Hs ( Z-9 ) is formed. In acetone solution, it rearranges to give the E isomer. Reaction of 8 with sulfur affords the bis(thioketene) complex C5H5(PiPr3)Rh(≡2-C,S; η2-C,S-S=C=CH-C6H4-CH=C=S)-Rh(PiPr3)C5H5 ( 12 ), for which only one diastereomer is observed. All attempts to prepare mononuclear rhodium compounds containing the diyne HC≡C-C6H4-G≡CH or the isomeric vinylidene: C=CH-C6H4-G≡CH as ligand failed. |
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