- Synthesis, characterization, and reactivity of rhodium(I) acetylacetonato complexes containing pyridinecarboxaldimine ligands
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Addition of o-C6H4NCH=NAr to Rh(coe) 2(acac) (coe = cis-cyclooctene, acac = acetylacetonato) gave several new iminopyridine rhodium(I) complexes of the type Rh(acac)(κ2- o-C6H4NCH=NAr) (1a Ar = 4-C6H4-OMe; 1b Ar = 2,6-C6H3-Me2; 1c Ar = 2,6-C 6H3-Et2; 1d Ar = 2,6-C6H 3-i-Pr2). All new rhodium complexes have been characterized by a number of physical methods, including multinuclear NMR spectroscopy and X-ray diffraction studies for 1b and 1c. Addition of CHCl 3 to 1a afforded the corresponding rhodium(III) complex trans-Rh(κ2-o-C6H4NCH=NAr)(CHCl 2)(Cl)(acac) (2). Addition of B2cat3 (cat = 1,2-O2C6H4) to 1 gave zwitterionic Rh(η6-catBcat)(κ2-o-C6H 4NCH=NAr) (3). The molecular structure of 3b has been confirmed by a single crystal X-ray diffraction study and shows that the N2Rh fragment is bound to the catBcat anion via one of the catecholato groups in a η6-fashion. These complexes have also been examined for their ability to catalyze the hydroboration of a series of vinylarenes. Reactions using catecholborane and pinacolborane seem to proceed largely through a dehydrogenative borylation mechanism to give a number of boronated products.
- Kanas, Diane A.,Geier, Stephen J.,Vogels, Christopher M.,Decken, Andreas,Westcott, Stephen A.
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p. 8727 - 8735
(2009/03/11)
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