[Pt(bipy)(ONO2)2] and [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4: Empirically identical but structurally distinct complexes obtained from a basic aqueous solution of [Pt(bipy)2](NO3)2

Warrick K.C. Lo; Rebecca J. Shepherd; Robert Stranger; Allan G. Blackman; Germán Cavigliasso

doi:10.1016/j.poly.2017.04.007

[Pt(bipy)(ONO₂)₂] and [{(bipy)Pt(μ-O₂NO)₂Pt(bipy)}₂](NO₃)₄: Empirically identical but structurally distinct complexes obtained from a basic aqueous solution of [Pt(bipy)₂](NO₃)₂

Warrick K.C. Lo, Rebecca J. Shepherd, Robert Stranger, Allan G. Blackman^*, Germán Cavigliasso

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

Vapour diffusion of acetonitrile into a basic aqueous solution of [Pt(bipy)₂](NO₃)₂·H₂O results in slow crystallisation of a mixture of the monomeric complex [Pt(bipy)(ONO₂)₂]·5.25H₂O and the tetrameric complex [{(bipy)Pt(μ-O₂NO)₂Pt(bipy)}₂](NO₃)₄·8.5H₂O, the structures of which were confirmed by X-ray crystallography. Calculations on the tetrameric complex show that the central Pt–Pt bond is weak, as evidenced by the fact that inclusion of dispersion forces is required to prevent the cation from dissociating into two [(bipy)Pt(μ-O₂NO)₂Pt(bipy)]²⁺ dimers. Isolation of the monomeric and tetrameric complexes shows that one of the bipy ligands in the [Pt(bipy)₂]²⁺ cation is easily displaced in basic aqueous solution. This displacement may be a consequence of OH⁻ attack at the Pt ion.

Original language	English
Pages (from-to)	145-153
Number of pages	9
Journal	Polyhedron
Volume	130
DOIs	https://doi.org/10.1016/j.poly.2017.04.007
Publication status	Published - 2017

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@article{9857d3aac6dc48e3a13cb2e2d7aace9f,

title = "[Pt(bipy)(ONO2)2] and [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4: Empirically identical but structurally distinct complexes obtained from a basic aqueous solution of [Pt(bipy)2](NO3)2",

abstract = "Vapour diffusion of acetonitrile into a basic aqueous solution of [Pt(bipy)2](NO3)2·H2O results in slow crystallisation of a mixture of the monomeric complex [Pt(bipy)(ONO2)2]·5.25H2O and the tetrameric complex [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4·8.5H2O, the structures of which were confirmed by X-ray crystallography. Calculations on the tetrameric complex show that the central Pt–Pt bond is weak, as evidenced by the fact that inclusion of dispersion forces is required to prevent the cation from dissociating into two [(bipy)Pt(μ-O2NO)2Pt(bipy)]2+ dimers. Isolation of the monomeric and tetrameric complexes shows that one of the bipy ligands in the [Pt(bipy)2]2+ cation is easily displaced in basic aqueous solution. This displacement may be a consequence of OH− attack at the Pt ion.",

keywords = "Bipyridine, Calculations, Five-coordinate, Platinum, Tetramer",

author = "Lo, {Warrick K.C.} and Shepherd, {Rebecca J.} and Robert Stranger and Blackman, {Allan G.} and Germ{\'a}n Cavigliasso",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier Ltd",

year = "2017",

doi = "10.1016/j.poly.2017.04.007",

language = "English",

volume = "130",

pages = "145--153",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

}

TY - JOUR

T1 - [Pt(bipy)(ONO2)2] and [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4

T2 - Empirically identical but structurally distinct complexes obtained from a basic aqueous solution of [Pt(bipy)2](NO3)2

AU - Lo, Warrick K.C.

AU - Shepherd, Rebecca J.

AU - Stranger, Robert

AU - Blackman, Allan G.

AU - Cavigliasso, Germán

PY - 2017

Y1 - 2017

N2 - Vapour diffusion of acetonitrile into a basic aqueous solution of [Pt(bipy)2](NO3)2·H2O results in slow crystallisation of a mixture of the monomeric complex [Pt(bipy)(ONO2)2]·5.25H2O and the tetrameric complex [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4·8.5H2O, the structures of which were confirmed by X-ray crystallography. Calculations on the tetrameric complex show that the central Pt–Pt bond is weak, as evidenced by the fact that inclusion of dispersion forces is required to prevent the cation from dissociating into two [(bipy)Pt(μ-O2NO)2Pt(bipy)]2+ dimers. Isolation of the monomeric and tetrameric complexes shows that one of the bipy ligands in the [Pt(bipy)2]2+ cation is easily displaced in basic aqueous solution. This displacement may be a consequence of OH− attack at the Pt ion.

AB - Vapour diffusion of acetonitrile into a basic aqueous solution of [Pt(bipy)2](NO3)2·H2O results in slow crystallisation of a mixture of the monomeric complex [Pt(bipy)(ONO2)2]·5.25H2O and the tetrameric complex [{(bipy)Pt(μ-O2NO)2Pt(bipy)}2](NO3)4·8.5H2O, the structures of which were confirmed by X-ray crystallography. Calculations on the tetrameric complex show that the central Pt–Pt bond is weak, as evidenced by the fact that inclusion of dispersion forces is required to prevent the cation from dissociating into two [(bipy)Pt(μ-O2NO)2Pt(bipy)]2+ dimers. Isolation of the monomeric and tetrameric complexes shows that one of the bipy ligands in the [Pt(bipy)2]2+ cation is easily displaced in basic aqueous solution. This displacement may be a consequence of OH− attack at the Pt ion.

KW - Bipyridine

KW - Calculations

KW - Five-coordinate

KW - Platinum

KW - Tetramer

UR - http://www.scopus.com/inward/record.url?scp=85018953872&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2017.04.007

DO - 10.1016/j.poly.2017.04.007

M3 - Article

SN - 0277-5387

VL - 130

SP - 145

EP - 153

JO - Polyhedron

JF - Polyhedron

ER -

[Pt(bipy)(ONO₂)₂] and [{(bipy)Pt(μ-O₂NO)₂Pt(bipy)}₂](NO₃)₄: Empirically identical but structurally distinct complexes obtained from a basic aqueous solution of [Pt(bipy)₂](NO₃)₂

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