Dynamic NMR expts. 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 mols. studied, with G.thermod. ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calcd. for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramol. P:OH-P interactions act as a mol. brake at room temp. Single-crystal x-ray diffraction confirms the presence of both intra and intermol. P:OH interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR anal. indicates a P-HCl- interaction in arom. or halogenated solvents which could have also a minor effect on the rotational barrier around the P(X)-Pt bond.
Multinuclear and Dynamic NMR Study of trans-[Pt(Cl)(PHCy2)2(PCy2)], [Pt(Cl)(PHCy2)3][BF4], [Pt(Cl)(PHCy2)3][Cl], trans-[Pt(Cl)(PHCy2)2{P(S)Cy2}], and trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}]. Influence of Intramolecular P=O···H-P and Cl···H-P Interactions on Restricted Rotation about Pt-P Bond. X-ray Structure of trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}]
FANIZZI, Francesco Paolo;
2005-01-01
Abstract
Dynamic NMR expts. 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 mols. studied, with G.thermod. ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calcd. for trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}] (4) where intramol. P:OH-P interactions act as a mol. brake at room temp. Single-crystal x-ray diffraction confirms the presence of both intra and intermol. P:OH interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR anal. indicates a P-HCl- interaction in arom. or halogenated solvents which could have also a minor effect on the rotational barrier around the P(X)-Pt bond.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
