Easily Prepared Chiral Scorpionates: Tris(2-oxazolinyl)boratoiridium(l) Compounds and Their Interactions with MeOtf
Optically active C{sub 3}-symmetric monoanionic ligands are uncommon in organometallic chemistry. Here we describe the synthesis of readily prepared tris(4S-isopropyl-2-oxazolinyl)phenylborate [To{sup P}] and fluxional, zwitterionic four- and five-coordinate iridium(I) compounds [Ir(To{sup P})-({eta}{sup 4}-C{sub 8}H{sub 12})] (4) and [?r(TO{sup P})(CO){sub 2} (5)]. The highly fluxional nature of 4 and 5 makes structural assignment difficult, and the interaction between the iridium(I) center and the [To{sup P}] ligand is established by solid-state and solution {sup 15}N NMR methods that permit the direct comparison between solution and solid-state structures. Although iridium cyclooctadiene 4 is a mixture of four- and five-coordinate species, the dicarbonyl 5 is only the five-coordinate isomer. The addition of electrophiles MeOTf and Mel provides the oxazoline N-methylated product rather than the iridium methyl oxidative addition product. N-Methylation was unequivocally proven by through-bond coupling observed in {sup 1}H-{sup 15}N HMBC experiments.
- Research Organization:
- Ames Lab., Ames, IA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- DE-AC02-07CH11358
- OSTI ID:
- 963281
- Report Number(s):
- IS-J 7316; TRN: US200917%%301
- Journal Information:
- Comments on Inorganic Chemistry, Vol. 47, Issue 22
- Country of Publication:
- United States
- Language:
- English
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