Rhodium Complexes of Tetradentate Tripodal Tripyridyl Ligands: Phosphate, Phosphate Monoester, and an Unexpected Acetimidamide Species
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Huang, R
Waghorn, CP
Christopher, TD
Söhnel, T
Chen, T
Blackman, AG
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Elsevier
Abstract
The complexes [Rh(N₄)Cl₂]ClO₄ (N₄ = tpa, pmea, pmap, tepa) and [Co(pmea)Cl₂]ClO₄ have been prepared and characterised (tpa = tris(2-pyridylmethyl)amine, pmea = bis[(2-pyridyl)methyl]-2-[(2-pyridyl)ethyl]amine, pmap = bis[2-(2-pyridyl)ethyl]-(2-pyridylmethyl)amine, and tepa = tris[2-(2-pyridyl)ethyl]amine), and the X-ray crystal structures of [Rh(pmea)Cl₂]ClO₄, [Co(pmea)Cl₂]ClO₄‧0.61H₂O, and [Rh(tepa)Cl₂]ClO₄ are reported. Reaction of the rhodium complexes with Na₃PO₄ and Na₂C₆H₅PO₄ gives chelated phosphate and phenylphosphate complexes for all but the [Rh(tpa)Cl₂]+ starting material, as evidenced by Hi Res Mass Spectrometry and ³¹P NMR spectroscopy. Reaction of the in situ-generated [Rh(pmap)Cl(MeCN)]²+ ion with bis(cyclohexylammonium)-t-butylphosphate gives [Rh(pmap)Cl(N-cyclohexylacetimidamide)](ClO₄)₂, which results from attack of cyclohexylamine at the nitrile C atom of coordinated MeCN. The X-ray crystal structure of this complex is reported.
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3402 Inorganic Chemistry, 34 Chemical Sciences, 0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0399 Other Chemical Sciences, Inorganic & Nuclear Chemistry, 3402 Inorganic chemistry, 3403 Macromolecular and materials chemistry
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Polyhedron, ISSN: 0277-5387 (Print); 1873-3719 (Online), Elsevier, 297, 118300-118300. doi: 10.1016/j.poly.2026.118300
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Creative Commons Attribution CC BY 4.0