EPR investigations of electronic structure of iron nitrosyl dithiophosphate complexes

✍ Scribed by B. Jezowska-Trzebiatowska; A. Jezierski; H. Kozłowski; N.D. Yordanov; D. Shopov

• Publisher: Elsevier Science
• Year: 1978
• Tongue: English
• Weight: 296 KB
• Volume: 31
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)94976-4

✦ Synopsis

Nitrosylironbis-di-iso-propyl-dithiophosphate complex and nitrosyliron-bis-dicyclohexyl-dithiophosphate complex, FeNO(dtp)z, were synthesized and studied by EPR. On the basis of frozen solution spectra 14N, 31P superhyperfine and "Fe hype&e parameters were obtained. The postulated electron conftguration a2(xy)2 b r (xz)2 b2(yz)2 a I(z2)' is suitable for interpretation of the all observed spin Hamiltonian parameters. The observed differences between parameters for the FeNO(dtp), and FeNO-(dtc)2 (dtc = dithiocarbamate anion) were interpreted by the influence of the out-of-plane rr-bonding with sulphur and increasing n*(NO) character of b, and b2 orbitals in the FeNO(dtp)2 complexes. Dinitrosyl complexes with the same ligands were obtained and investigated by EPR; for the complexes, similarly to those of mononitrosyls, we found a characteristic positive sign of A,("Fe) values whereas A,&'Fe)

is negative.