Complexes of Ambidentate N,O-Donor Ligands with Rhenium(I) and -(V)

• Published in: Journal of chemical crystallography 2018-09, Vol.48 (3), p.96-102
• Main Authors: Boyce, Annemè, Gerber, Thomas I. A., Hosten, Eric C.
• Format: Article
• Language: English
• Subjects: Acetonitrile; Chelates; Chemistry; Chemistry and Materials Science; Coordination compounds; Crystal structure; Crystallography and Scattering Methods; Diffraction; Ethanol; Hydroxypicolinic acid; Inorganic Chemistry; Ligands; Organometallic Chemistry; Original Paper; Physical Chemistry; Rhenium
• ISSN: 1074-1542; 1572-8854
• DOI: 10.1007/s10870-018-0715-5

The reaction of the potentially bidentate ambidentate N,O-donor ligands 3-hydroxy-2-pyridinecarboxylic acid (Hhpc) and 3-hydroxy-2-(hydroxymethyl)pyridine (Hhhp) with trans -[ReOCl 3 (PPh 3 ) 2 ] led to the isolation of the products [ReOCl(hpc) 2 ] ( 1 ) (from acetonitrile) and [ReOCl 2 (hhp)(PPh 3 )] ( 2 ) (from ethanol) respectively. In both complexes hpc and hhp are coordinated as bidentate N,O-donor chelates, rather than as O,O-donor ligands. From the reaction of [Re(CO) 5 Cl] and Hhhp·HCl in ethanol the neutral complex fac -[Re(CO) 3 Cl(Hhhp)] ( 3 ) was obtained, with N,O-coordination of Hhhp. Complex 1 crystallizes in the monoclinic space group P 2 1 /n with a  = 6.8782(3), b  = 20.0647(8), c  = 10.8692(4) Å, β  = 107.545(1)°, and Z  = 4. Complex 2 crystallizes in the triclinic space group P -1 with a  = 7.3523(4), b  = 8.1047(5), c  = 19.591(1) Å, α  = 91.133(2)°, β  = 93.656(2)°, γ  = 93.074(2)° and Z  = 2. Complex 3 has monoclinic P 2 1 /c symmetry with the cell parameters a  = 10.6452(5), b  = 11.1372(5), c  = 9.7229(5) Å, β  = 106.107(2)°, and Z  = 4. Graphical Abstract The reaction of the potentially bidentate ambidentate N,O-donor ligands 3-hydroxy-2-pyridinecarboxylic acid (Hhpc) and 3-hydroxy-2-(hydroxymethyl)pyridine (Hhhp) with trans -[ReOCl 3 (PPh 3 ) 2 ] led to the isolation of the products [ReOCl(hpc) 2 ] (from acetonitrile) and [ReOCl 2 (hhp)(PPh 3 )] (from ethanol) respectively. In both complexes hpc and hhp are coordinated as bidentate N,O-donor chelates, rather than as O,O-donor ligands. From the reaction of [Re(CO) 5 Cl] and Hhhp·HCl in ethanol the neutral complex fac -[Re(CO) 3 Cl(Hhhp)] was obtained, with N,O-coordination of Hhhp. Spectroscopic data and the X-ray crystal structures of the complexes are reported.