Lanthanide complexes oxygen donors

Complexes of the lanthanides with neutral oxygen donor ligands. D. K. Koppikar, P. V. Sivapul-laiah, L. Ramakrishnan and S. Soundararajan, Struct. Bonding (Berlin), 1978, 34,135-213 (406). 

Koppikar DK, Sivapullaiah PV, Ramakrishnan L, Soundararajan S (1978) Complexes of the Lanthanides with Neutral Oxygen Donor Ligands. 34 135-213 Keren B, see Valach F (1984) 55 101-151... 

Complexes of the Lanthanides with Neutral Oxygen Donor Ligands... 

Probably, the first series of lanthanide complexes with neutral oxygen donor ligands is that of AP with the lanthanide nitrates. In 1913, Kolb (79) reported tris-AP complexes with lighter lanthanide nitrates and tetrakis-AP complexes with heavier lanthanide nitrates. Subsequently, complexes of lanthanide nitrates with AP which have a L M of 6 1 and 3 1 have also been prepared (80-82). Bhandary et al. (83) have recently shown through an X-ray crystal and molecular structure study of Nd(AP)3(N03)3 that all the nitrates are bidentate and hence the coordination number for Nd(III) is nine in this complex. Complexes of AP with lanthanide perchlorates (81, 84), iodides (81, 85), and isothiocyanates (66, 86, 87) are known. While the perchlorates and iodides in the respective complexes remain ionic, two of the isothiocyanates are coordinated in the corresponding complexes of AP with lanthanide isothiocyanates. 

General aspects of the coordination chemistry of the lanthanides with reference to the complexes of neutral oxygen donor ligands are dealt with in this section. For con venience, this section is subdivided into three parts 1. synthetic procedures, 2. stoichiometry, and 3. coordination numbers and coordination polyhedra. 

So far almost all the complexes of the lanthanides with neutral oxygen donor ligands have been prepared from hydrated salts. Quite a few of these complexes have one to three molecules of water in their composition. The coordinated or noncoor-dinated nature of water in these complexes is not well established. 

Useful structural data have been obtained from single crystal X-ray diffraction methods for a number of lanthanide complexes (15,17). In this section, the structures of various complexes with neutral oxygen donor ligands which have been studied by single crystal X-ray diffraction methods are described. For convenience, the structures are discussed in terms of coordination numbers of the lanthanide ions. 

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