Formation of heterobinuclear Pt-Au complexes by chelate ring-opening of cis-[Pt(κ2-C6R4PPh2)2] (R = H, F)

N. Mirzadeh; M. A. Bennett; E. Wächtler; L. Zhechkov; T. Heine; S. K. Bhargava

doi:10.1016/j.jorganchem.2015.02.009

Formation of heterobinuclear Pt-Au complexes by chelate ring-opening of cis-[Pt(κ²-C₆R₄PPh₂)₂] (R = H, F)

N. Mirzadeh, M. A. Bennett, E. Wächtler, L. Zhechkov, T. Heine, S. K. Bhargava^*

^*Corresponding author for this work

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

5 Citations (Scopus)

Abstract

Mixed metal complexes of the type [Pt(κ²-2-C₆R₄PPh₂) (PPh₃) (μ-2-C₆R₄PPh₂)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ²-C₆R₄PPh₂)₂] with [AuCl(PPh₃)]. Under similar reaction conditions, the trans isomer of [Pt(κ²-C₆F₄PPh₂)₂] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ²-2-C₆R₄PPh₂)₂] is favoured over nucleophilic addition of PPh₃ to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ²-2-C₆R₄PPh₂)₂] in forming the mixed metal Pt-Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt-P bonds in the cis isomer are more labile.

Original language	English
Pages (from-to)	130-134
Number of pages	5
Journal	Journal of Organometallic Chemistry
Volume	783
DOIs	https://doi.org/10.1016/j.jorganchem.2015.02.009
Publication status	Published - 1 May 2015

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title = "Formation of heterobinuclear Pt-Au complexes by chelate ring-opening of cis-[Pt(κ2-C6R4PPh2)2] (R = H, F)",

abstract = "Mixed metal complexes of the type [Pt(κ2-2-C6R4PPh2) (PPh3) (μ-2-C6R4PPh2)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ2-C6R4PPh2)2] with [AuCl(PPh3)]. Under similar reaction conditions, the trans isomer of [Pt(κ2-C6F4PPh2)2] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ2-2-C6R4PPh2)2] is favoured over nucleophilic addition of PPh3 to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ2-2-C6R4PPh2)2] in forming the mixed metal Pt-Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt-P bonds in the cis isomer are more labile.",

keywords = "Gold, Mixed metal complexes, Platinum, Ring opening",

author = "N. Mirzadeh and Bennett, {M. A.} and E. W{\"a}chtler and L. Zhechkov and T. Heine and Bhargava, {S. K.}",

year = "2015",

month = may,

day = "1",

doi = "10.1016/j.jorganchem.2015.02.009",

language = "English",

volume = "783",

pages = "130--134",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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T1 - Formation of heterobinuclear Pt-Au complexes by chelate ring-opening of cis-[Pt(κ2-C6R4PPh2)2] (R = H, F)

AU - Mirzadeh, N.

AU - Bennett, M. A.

AU - Wächtler, E.

AU - Zhechkov, L.

AU - Heine, T.

AU - Bhargava, S. K.

PY - 2015/5/1

Y1 - 2015/5/1

N2 - Mixed metal complexes of the type [Pt(κ2-2-C6R4PPh2) (PPh3) (μ-2-C6R4PPh2)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ2-C6R4PPh2)2] with [AuCl(PPh3)]. Under similar reaction conditions, the trans isomer of [Pt(κ2-C6F4PPh2)2] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ2-2-C6R4PPh2)2] is favoured over nucleophilic addition of PPh3 to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ2-2-C6R4PPh2)2] in forming the mixed metal Pt-Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt-P bonds in the cis isomer are more labile.

AB - Mixed metal complexes of the type [Pt(κ2-2-C6R4PPh2) (PPh3) (μ-2-C6R4PPh2)AuCl] (R = H, F) can be prepared by treatment of cis-[Pt(κ2-C6R4PPh2)2] with [AuCl(PPh3)]. Under similar reaction conditions, the trans isomer of [Pt(κ2-C6F4PPh2)2] is unreactive. Computational studies have been performed to provide insights into the reasons for this difference in reactivity. Density Functional Theory (DFT) calculations show that formation of an AuCl adduct of [Pt(κ2-2-C6R4PPh2)2] is favoured over nucleophilic addition of PPh3 to Pt as the initial step of the reaction, and reveal the required energy of the cis and trans isomers of the bis-chelate [Pt(κ2-2-C6R4PPh2)2] in forming the mixed metal Pt-Au compounds. NBO analysis sheds more light on the bonding orbitals of the cis and trans isomers, suggesting that the Pt-P bonds in the cis isomer are more labile.

KW - Gold

KW - Mixed metal complexes

KW - Platinum

KW - Ring opening

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U2 - 10.1016/j.jorganchem.2015.02.009

DO - 10.1016/j.jorganchem.2015.02.009

M3 - Article

SN - 0022-328X

VL - 783

SP - 130

EP - 134

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Formation of heterobinuclear Pt-Au complexes by chelate ring-opening of cis-[Pt(κ²-C₆R₄PPh₂)₂] (R = H, F)

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