Tyrone P. Jeynes, M. Cifuentes, M. Humphrey
Aug 23, 1994
Citations
0
Influential Citations
5
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract The reaction between 4-methoxyphenol and Ru 3 (CO) 12 in cyclohexane has been investigated and found to afford a hexaruthenium ‘raft’ cluster Ru 6 (μ-H) 2 (μ 5 -η 7 -OC 6 H 3 OMe-4)(CO) 16 ( 3a ), together with tetraruthenium clusters incorporating three (Ru 4 (μ 3 -OC 6 H 4 OMe-4) 2 (μ-Cl)(μ-OC 6 H 4 OMe-4)(CO) 10 ( 3b )) or four (Ru 4 (μ 3 -OC 6 H 4 OMe-4) 2 (μ-OC 6 H 4 OMe-4) 2 (CO) 10 ( 3c )) aryloxo ligands; similarly, reaction of Ru 3 (CO) 12 with 2-naphthol afforded the analogous Ru 6 (μ-H) 2 (μ 5 -η 7 -OC 10 H 6 )(CO) 16 ( 4a ), Ru 4 (μ 3 -OC 10 H 7 ) 2 (μ-Cl)(μ-OC 10 H 7 )(CO) 10 ( 4b ) and Ru 4 (μ 3 -OC 10 H 7 ) 2 (μ-OC 10 H 7 ) 2 (CO) 10 ( 4c ). The source of chloride in 3b and 4b is believed to be carbon tetrachloride contaminant in the cyclohexane. An X-ray diffraction study reveals that 3b contains an Ru 3 (CO) 8 unit linked to an Ru(CO) 2 moiety by two asymmetric triply-bridging and one asymmetric doubly-bridging 4-methoxyphenoxo ligands, and an asymmetric doubly-bridging chloro ligand; this interaction is strongly suggestive of a higher oxidation state ruthenium linked to a trinuclear cluster of formally zero oxidation state. The dynamic 13 C NMR spectra of 4c have been recorded, and are consistent with restricted rotation about the ArO linkage of the μ 2 -coordinated naphthoxo ligands at low temperature.