ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Electronic structure and chemical bonding in cyanonitrosyl complexes of transition metals

B. Jeźowska-Trzebiatowska and J. Ziólkowski

Department of Inorganic Chemistry, University of Wroclaw, Poland

Abstract: The electronic structure of central ions in complexes of the [M(CN)₅NO]^n- type and the character of metal-ligand bond were described by applying radioisotopic exchange and ir spectra methods. Kinetics of the isotopic exchange reactions in the system [M(CN)₅NO]^n- - ¹⁴CN^- (M = Cr, Mn, Fe, and Co) showed that the central ions are effectively trivalent. The stabilization of the metal oxidn. state in the pentacyanonitrosyl complexes of Cr, Mn, and Fe as compared with hexacyano complexes is due to the increase of stability of the M-NO bond because of the addnl. π-bond (of the dative or covalent type). The appearance of π-bond M-NO alongside the σ-bond was proven in the complexes of Cr, Mn, and Fe by detns. of kinetics and mechanism of exchange reaction and by the anal. of ir spectra. The ir spectra demonstrated a close relationship between the values and positions of the frequency characteristics for N-O and M-N fundamental vibrations and π- and σbond participation on M-N and N-O bonding. The construction of a general model of coordination in the NO group of the pentacyanonitrosyl complexes of the first transition metal series is shown.

Full paper in Portable Document Format: 193a177.pdf

Chemical Papers 19 (3) 177–185 (1965)