title: 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)Cy(2)]], 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]].
abstract: 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 deltaG++ 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 P=O...H-P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular P=O...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.
authors.affiliation: Dipartimento di Ingegneria delle Acque e di Chimica del Politecnico di Bari, via Orabona 4, I-70125 Bari, Italy. p.mastrorilli@poliba.it
authors.forename: Piero
authors.initials: P
authors.lastname: Mastrorilli
authors.forename: Cosimo F
authors.initials: CF
authors.lastname: Nobile
authors.forename: Mario
authors.initials: M
authors.lastname: Latronico
authors.forename: Vito
authors.initials: V
authors.lastname: Gallo
authors.forename: Ulli
authors.initials: U
authors.lastname: Englert
authors.forename: Francesco P
authors.initials: FP
authors.lastname: Fanizzi
authors.forename: Oronzo
authors.initials: O
authors.lastname: Sciacovelli
mesh_terms: D002412:Cations; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D017671:Platinum Compounds / Q000737:chemistry*
chemical_list: D002412:Cations; D017671:Platinum Compounds