High-Nuclearity Osmium Carbonyl Cluster Complexes Containing (6-Methylpyrid-2-yl)imido Ligands. Synthesis of Hepta-, Octa-, and Nonanuclear Derivatives
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- 作者：Javier A. Cabeza ; Ignacio del Rí ; o ; Pablo Garcí ; a-Á ; lvarez ; Daniel Miguel
- 刊名：Organometallics
- 出版年：2007
- 出版时间：June 18, 2007
- 年：2007
- 卷：26
- 期：13
- 页码：3212 - 3216
- 全文大小：143K
- 年卷期：v.26,no.13(June 18, 2007)
- ISSN：1520-6041
文摘
Three high-nuclearity osmium carbonyl cluster complexes, [Os7(
r.gif">5-
rs/kappa.gif" BORDER=0 >2-ampy)(r.gif">-CO)2(CO)17] (1), [Os8(r.gif">3-H)(r.gif">-H)(r.gif">5-rs/kappa.gif" BORDER=0 >2-ampy)(r.gif">-CO)(CO)19] (2), and [Os9O(r.gif">4-rs/kappa.gif" BORDER=0 >2-ampy)2(CO)18] (3) (H2ampy = 2-amino-6-methylpyridine), have been prepared by heating [Os3(CO)12] with 0.5 equiv of H2ampy in decane atreflux temperature. The trinuclear complex [Os3(r.gif">-H)(r.gif">3-rs/kappa.gif" BORDER=0 >2-Hampy)(CO)9] is an intermediate in thisreaction. The metallic skeletons of 1 and 2 can be described as mono- (1) or bi-face-capped (2), basal-edge-bridged, square pyramids, whereas that of compound 3 consists of a pentagonal bipyramid withtwo equatorial edges spanned by metal atoms. In the three clusters, the ampy ligands are attached toedge-bridging Ru atoms through their pyridine N atoms, while they also cap metallic squares (in 1 and2) or triangles (in 3) through their imido N atom. An additional feature of compound 3 is that it containsa terminal oxo ligand, unprecedented in osmium carbonyl cluster chemistry.
r.gif">5-rs/kappa.gif" BORDER=0 >2-ampy)(r.gif">-CO)2(CO)17] (1), [Os8(r.gif">3-H)(r.gif">-H)(r.gif">5-rs/kappa.gif" BORDER=0 >2-ampy)(r.gif">-CO)(CO)19] (2), and [Os9O(r.gif">4-rs/kappa.gif" BORDER=0 >2-ampy)2(CO)18] (3) (H2ampy = 2-amino-6-methylpyridine), have been prepared by heating [Os3(CO)12] with 0.5 equiv of H2ampy in decane atreflux temperature. The trinuclear complex [Os3(r.gif">-H)(r.gif">3-rs/kappa.gif" BORDER=0 >2-Hampy)(CO)9] is an intermediate in thisreaction. The metallic skeletons of 1 and 2 can be described as mono- (1) or bi-face-capped (2), basal-edge-bridged, square pyramids, whereas that of compound 3 consists of a pentagonal bipyramid withtwo equatorial edges spanned by metal atoms. In the three clusters, the ampy ligands are attached toedge-bridging Ru atoms through their pyridine N atoms, while they also cap metallic squares (in 1 and2) or triangles (in 3) through their imido N atom. An additional feature of compound 3 is that it containsa terminal oxo ligand, unprecedented in osmium carbonyl cluster chemistry.