Heterotridentate Organomonophosphines in Pt(κ3–X1P1X2)(Y) (X1,2 = N1,2 or S1,2), Pt(κ3–P1N1X1)(Y) (X1 = O, C, S or Se) Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL)—Structural Aspects

Abstract

This review covers twenty four Pt(II) complexes of the inner coordination sphere Pt(κ3–P1 N1N2)(Y), (Y = Cl, CL); Pt(κ3–P1N1X1)(Y), (X1 = O1 and Y = P2L, Cl, I); (X1 = C1 and Y = NL, Cl); (X1 = S1 and Y = Cl, I); (X1 = Se1 and Y = Cl); Pt(κ3–N1P1N2)(Cl), Pt(κ3–S1P1S2)(Cl), Pt(κ3–P1S1Cl1)(Cl) and Pt(κ3–P1Si1N1)(OL). These complexes are crystallized in three crystal classes: monoclinic (16 examples), triclinic (5 examples), and orthorhombic (3 examples). Each κ3–ligand creates two metallocyclic rings with various combinations of the respective metallocyclic rings. If the common central ligating atom is N1, the 5 + 5 membered, 5 + 5, 5 + 6, 6 + 5, and 6 + 6; if the common central ligating atom is P1: 5 + 5, and 6 + 6; if the common central ligating atom is S1 or Si1, 5 + 6-membered. The structural parameters (Pt-L, L-Pt-L) are analysed and discussed with an attention to the distortion of a square-planar geometry about the Pt(II) atoms as well as trans-influence. The sums of the Pt-L (x = 4) bond distances the growing with the covalent radius of the Y atoms. Noticeably, the distortion of the square-planar geometry is growing with the decreasing size of the inner coordination sphere about the Pt(II) atom. There is a relation between the degree of distortion (Ʈ4) and the numbers of the metallocycles rings. The distortion diminishing is in the order of: 0.058 (5 + 5) > 0.037 (6 + 5) > 0.023 (5 + 6) > 0.022 (6 + 6) membered.