Synthesis, structure, and coordination chemistry of a tridentate, six-electron-donor amidinate ligand

Journal Article · Mon Dec 06 04:00:00 UTC 1999 · Organometallics

DOI:https://doi.org/10.1021/om990365w· OSTI ID:20013623

Kincaid, K; Gerlach, C P; Giesbrecht, G R; Hagadorn, J R; Whitener, G D; Shafir, A; Arnold, J

The coordination chemistry of ancillary amidinate ligands with a pendant pyridine functionality is described. Reaction of p-toluoyl- or p-tBu benzoyl chloride with 2-amino-ethylpyridine generates the amides 2-Py-(CH{sub 2}){sub 2}NHCO(p-RPh) (R = Me 1a tBu 1b); these amides are then converted to the amidines 2-Py-(CH{sub 2}){sub 2}NHC(p-RPh)NR{prime} (R = Me, R{prime} = Ph (2a) (L{sup Me}H); R = tBu, R{prime} = 3,5-dimethylphenyl (2b) (L{sup tBu}H)) by reaction with PCl{sub 5} followed by R{prime}NH{sub 2}. The amidines 2a,b were characterized by {sup 1}H NMR and IR spectroscopy and elemental analyses, and 2b was characterized by X-ray crystallography. Reaction of 2a or 2b with homoleptic metal-alkyls or -amides yields the mono- or bis(amidinate) complexes (L{sup Me}){sub 2}Mg (3a), (L{sup tBu})AlMe{sub 2} (4), (L{sup tBu})Zr(CH{sub 2}Ph){sub 3} (5), and (L{sup Me}){sub 2}La[N(SiMe{sub 3}){sub 2}] (6). All metal complexes were characterized by {sup 1}H NMR and IR spectroscopy, elemental analyses, and X-ray crystallography. The X-ray crystal structures of compounds 3--6 show them to be monomeric, with the pendant pyridine coordinates intramolecularly in all cases. The tridentate amidinate coordinates meridionally to the metal center except in the case of the lanthanum derivative 6, where an approximate facial geometry is observed.

• Research Organization: Univ. of California, Berkeley, CA (US); Lawrence Berkeley National Lab., CA (US)
• Sponsoring Organization: US Department of Energy
• OSTI ID: 20013623
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 25 Vol. 18; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ALUMINIUM COMPLEXES
AMIDINES
LANTHANUM COMPLEXES
LIGANDS
MAGNESIUM COMPLEXES
PYRIDINES