Steric Modification of M-P Bond Lengths: Crystal and Molecular-Structures of the Platinum(II) Complexes trans-(PPr^I₃)₂Cl_nH_2-nPt^II (N = 0-2)

Abstract

Crystal structure analyses of the square-planar platinum complexes trans-(PPrⁱ₃)₂Cl_nH_2-nPt^II(n = 0-2) (C), (B), (A) are described. Diffraction data were recorded at room temperature with a Picker FACS-1 diffractometer. Convergence R values, for reflection numbers given in parentheses, are 0.020 (2373), (A), 0.021 (5771), (B) and 0.018 (1982), (C). The ligand conformation about the Pt-P bonds is perpendicular for (A) and (B) and eclipsed for (C). The Pt-P distances decrease systematically with increasing hydride content [2.339(1)Ǻ, (A); 2.286(1)Ǻ, (B); 2.252(1)Ǻ, (C)]. The decrease reflects the low steric requirement of hydride vis a vis chloride ligands and concomitant changes in anionic ligand/phosphine substituent non-bonding interactions. The trans-bond lengthening of the Pt- Cl bond in (B)(due to trans hydride) is 0.092(1)Ǻ.