Synthesis and reactions of Ru(CH2)Cl(NO)(PPh3)2, a stable terminal methylene complex and the crystal structure of Ru(CH2PPh3)(η2-C2F4)Cl(NO)(PPh3)
- 1 January 1991
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. S,p. 609-614
- https://doi.org/10.1039/dt9910000609
Abstract
Treatment of RuCl(NO)(PPh3)2 with CH2N2 in diethyl ether at room temperature affords Ru(CH2)Cl(N)(PPh3)21. Complex 1 undergoes a reaction with each of the reagents HCl, [Aul2]–, HgCl(C6H4Me-p), HgCl2 and SO2 forming respectively RuMeCl2(NO)(PPh3)22, [graphic omitted]ul)Cl(NO)(PPh3)23, Ru[CH2Hg(C6H4Me-p)]Cl2(NO)(PPh3)24a, Ru(CH2HgCl)Cl2(NO)(PPh3)24b and [graphic omitted]]Cl(NO)(PPh3)25. Treatment of 1 with PhC2Ph at room temperature affords the unstable complex Ru(CH2PPh3)(η2-PhC2Ph)Cl(NO)(PPh3)6. Reaction of 1 with ethylene under the same conditions gives, as a final product, Ru(η2-C2H4)Cl(NO)(PPh3)211. An NMR investigation of the production of 11 confirmed the presence of the intermediate Ru(CH2PPh3)(η2-C2H4)Cl(NO)(PPh3)10, and the formation of propene as 11 was generated, suggesting a possible metallacyclopropane intermediate. In contrast, treatment of 1 with C2F4 yields Ru(CH2PPh3)(η2-C2F4)Cl(NO)(PPh3)7, exclusively, the structure of which was confirmed by single-crystal X-ray diffraction. The metal geometry is that of a distorted trigonal bipyramid, with the triphenylphosphine and the ylide carbon occupying the apical sites. The osmium analogue of 7, Os(CH2PPh3)(η2-C2F4)Cl(NO)(PPh3)8, is obtained from a similar reaction.Keywords
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