Reactions of cyano(alkynyl)ethenes with some alkynyl- and diynyl-ruthenium complexes |
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Authors: | David J Armitt Brian W Skelton |
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Institution: | a School of Chemistry and Physics, University of Adelaide, Adelaide, South Australia 5005, Australia b Chemistry M313, SBBCS, University of Western Australia, Crawley, Western Australia 6009, Australia |
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Abstract: | Reactions of Ru(CCPh)(PPh3)2Cp with (NC)2CCR1R2 (R1 = H, R2 = CCSiPri38; R1 = R2 = CCPh 9) have given η3-butadienyl complexes Ru{η3-CC(CN)2]CPhCR1R2}(PPh3)Cp (11, 12), respectively, by formal 2 + 2]-cycloaddition of the alkynyl and alkene, followed by ring-opening of the resulting cyclobutenyl (not detected) and displacement of a PPh3 ligand. Deprotection (tbaf) of 11 and subsequent reactions with RuCl(dppe)Cp and AuCl(PPh3) afforded binuclear derivatives Ru{η3-CC(CN)2]CPhCHCCMLn]}(PPh3)Cp MLn = Ru(dppe)Cp 19, Au(PPh3) 20]. Reactions between 8 and Ru(CCCCR)(PP)Cp PP = (PPh3)2, R = Ph, SiMe3, SiPri3; PP = dppe, R = Ph] gave η1-dienynyl complexes Ru{CCCC(CN)2]CRCHCC(SiPri3)]}(PP)Cp (15-18), respectively, in reactions not involving phosphine ligand displacement. The phthalodinitrile C6H(CCSiMe3)(CN)2(NH2)(SiMe3) 10 was obtained serendipitously from (Me3SiCC)2CO and CH2(CN)2, as shown by an XRD structure determination. The XRD structures of precursor 7 and adducts 11, 12 and 17 are also reported. |
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Keywords: | Cyanocarbon Ruthenium Cyclo-addition Alkynyl Diynyl XRD structure |
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