Synthesis and structure of lanthanide complexes derived from the O,N-chelating, bis(methylpyridine)-substituted alcohol HOC(CMe{sub 3})(2-CH{sub 2}NC{sub 5}H{sub 3}Me-6){sub 2}
- Univ. of California, Irvine, CA (United States)
Hydrolysis of the product formed by reacting 2 equiv of 2-(lithiomethylene)-6-methylpyridine with trimethylacetyl chloride gives the alcohol HOC(CMe{sub 3})(2-CH{sub 2}NC{sub 5}H{sub 3}Me-6){sub 2}, (1) (HOR), in 44% yield. Three equivalents of (1) reacts with Yb[N(SiMe{sub 3}){sub 2}]{sub 3} to form Yb(OR){sub 3} (2a). The analogous 2 equiv reaction generates Yb(OR){sub 2}[N(SiMe{sub 3}){sub 2}], (3). X-ray diffraction studies were successful on (3) and on (2b), the Sm analog of (2a). Two of the alkoxide ligands in Sm(OR){sub 3}, (2b), are bidentate such that each has an uncomplexed nitrogen donor atom oriented away from the metal. These chelates occupy basal positions in the distorted square pyramidal geometry around the metal center in (2b) such that the oxygen donors are trans. The axial position is occupied by the third alkoxide which is monodentate through its oxygen donor atom. This leaves a total of four unattached pyridine functionalities available for further coordination. The ligand arrangement in (3) is very similiar to that in (2b) except that the monodentate alkoxide in (2b) is replaced by a N(SiMe{sub 3}){sub 2} group. A ligand fragmentation product, (R{prime}O){sub 2}Sm({mu}-OR){sub 2}Na, (4), containing the chelating bidentate pyridine enolate ligand [OC(CMe{sub 3})(=2CHNC{sub 5}H{sub 3}Me-6)](OR{prime}), formed by loss of a 2,6-dimethylpyridine group from OR, was also isolated in the course of these studies. Each OR ligand in (4) has its oxygen atom bridging Sm and Na, one pyridine nitrogen coordinated to Na, and one pyridine nitrogen which is not connected to any metal. The samarium center in (4) has a distorted octahedral geometry generated by two chelating R{prime}O groups and the two bridging oxygens from the OR groups. The nitrogen donor atoms of the R{prime}O groups have a cis orientation and are trans to the bridging ligands.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 502042
- Journal Information:
- Inorganic Chemistry, Vol. 34, Issue 14; Other Information: PBD: 5 Jul 1995
- Country of Publication:
- United States
- Language:
- English
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