Platinum organometallic complexes: classification and analysis of crystallographic and structural data for dimeric complexes

Abstract

AbstractThis review covers over 260 examples of dimeric organoplatinum complexes. Platinum is predominantly found in the oxidation states +2 and +4, but with some examples of 0, +1, +2.5, +3, and of mixed-valence as well. A number of coordination state geometries are observed, of which the most common is essentially square-planar at Pt(II), a distorted octahedral at Pt(IV), and some examples of trigonal planar and trigonal bipyramidal as well. The most common ligands are methyl (Me), carbonyl and PX3. The shortest Pt-Pt bond distance is 245.1(1) pm. The mean Pt-Pt bond distance increases in the order: 261.1 pm [Pt(2.5)-Pt(2.5)]<261.3 pm [Pt(III)-Pt(III)]<262.4 pm [Pt(I)-Pt(I)]<270.3 pm [Ot(II)-Pt(II)]<277.2 pm [Pt(0)-Pt(0)]<282.6 pm [Pt(II)-Pt(II)]. The Pt…Pt no-bonding distances are: Pt(II)…Pt(II), 3.008–17.959 pm; Pt(IV)…Pt(IV), 327.5–768.0 pm; Pt(II)-Pt(0), 378.6 pm and Pt(II)…Pt(IV), 389 pm. There are several relationships pointed out between the Pt-Pt distances, Pt-X-Pt bridge angles and covalent radii of coordinated atoms. Several examples contain two crystallographically independent molecules within the same crystal, differing mostly by degree of distortion, which are examples of distortion isomerism.