Multinuclear and Dynamic NMR Study of <i>trans</i>-[Pt(Cl)(PHCy<sub>2</sub>)<sub>2</sub>(PCy<sub>2</sub>)], [Pt(Cl)(PHCy<sub>2</sub>)<sub>3</sub>][BF<sub>4</sub>], [Pt(Cl)(PHCy<sub>2</sub>)<sub>3</sub>][Cl], <i>trans</i>-[Pt(Cl)(PHCy<sub>2</sub>)<sub>2</sub>{P(S)Cy<sub>2</sub>}], and <i>trans</i>-[Pt(Cl)(PHCy<sub>2</sub>)<sub>2</sub>{P(O)Cy<sub>2</sub>}]. Influence of Intramolecular PO···H−P and Cl···H−P Interactions on Restricted Rotation about Pt−P Bond. X-ray Structure of <i>trans</i>-[Pt(Cl)(PHCy<sub>2</sub>)<sub>2</sub>{P(O)Cy<sub>2</sub>}]
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Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2{P(X)Cy2}]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)−Pt bond is hindered for all molecules studied, with ΔG⧧ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramolecular PO···H−P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular PO···H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P−H···Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the rotational barrier around the P(X)−Pt bond.
