Structural aspects of Pt(η³-X¹N¹X²)(PL) (X^1,2 = O, C, or Se) and Pt(η³-N¹N²X¹)(PL) (X¹ = C, S, or Se) derivatives

Abstract

This article covers 26 Pt(ii) complexes of compositions Pt(η3-X1N1X2)(PL) (X1,2 = O, C, or Se) and Pt(η3-N1N2X1)(PL) (X1 = C, S, or Se). These complexes crystallized in two crystal classes: monoclinic (14 examples) and triclinic (12 examples). The heterotridentate ligand with monodentate PL builds up a distorted square-planar geometry around each Pt(ii) atom. Each heterotridentate ligand Pt(η3-X1N1X2)(PL) creates two metallocyclic rings with a common N1 atom of the O1C2N1C3O2, O1C3N1C3O2, O1C2NN1C3O2, C1C2N1C2C2, and Se1C2N1NC2Se2 types. In Pt(η3-N1N2X1)(PL) complexes, the tridentate ligand with a common N2 atom forms the following types of metallocyclic rings: N1C2N2C2C1, N1C2N2NCS1, and N1CNN2NCSe1. The total mean values of τ4 for respective complexes as it grows in the sequence: 0.056 (Pt(η3-O1N1O2)(PL)) < 0.091 (Pt(η3-Se1N1Se2)(PL)) < 0.161 (Pt(η3-N1N2S1)(PL)) < 0.174 (Pt(η3-N1N2Se1)(PL)) < 0.188 (Pt(η3-C1N1C2)(PL)) < 0.211 (Pt(η3-N1N2C1)(PL)). The distortion of the square-planar geometry increases in the given sequences. The structural data (Pt–L, L–Pt–L) are analyzed and discussed with attention to the distortion of a square-planar geometry about the Pt(ii) atoms as well as of trans-influence.