Abstract
Using 2D proton-coupled gHSQC pulse sequences in addition to 1D 15N NMR experiments of 15N labeled systems, 15N NMR chemical shifts of a range of transition metal amido and amine complexes were determined. Tungsten(II), ruthenium(II), platinum(IV) and copper(I) complexes with aniline and their anilido variants were studied and compared to free aniline, lithium anilido and anilinium tetrafluoroborate. Upon coordination of aniline to transition metals, upfield chemical shifts of 20-60 ppm were observed. Deprotonation of the amine complexes to form amido complexes resulted in downfield chemical shifts of 40-60 ppm for all of the complexes except for the tungsten d4 system. For the tungsten(II) complexes, the cationic aniline complex displayed a downfield shift of approximately 56 ppm relative to the neutral anilido complex. The change in chemical shift for amine to amido conversion is proposed to depend on the ability of the amido ligand to π-bond with the metal center, which influences the magnitude of the paramagnetic screening term.
Original language | English (US) |
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Pages (from-to) | 1549-1556 |
Number of pages | 8 |
Journal | Journal of Organometallic Chemistry |
Volume | 694 |
Issue number | 9-10 |
DOIs | |
State | Published - Apr 15 2009 |
Externally published | Yes |
Keywords
- N NMR spectroscopy
- Amido
- Amine
- Transition metals
ASJC Scopus subject areas
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry