Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]

Siew Huay Chong; William Henderson; T S Andy Hor

doi:10.1039/b707526j

Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]

Siew Huay Chong, William Henderson, T S Andy Hor

Chemistry

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

23 Citations (Scopus)

Abstract

The normally robust monoalkylated complexes [Pt₂(µ-S)(µ-SR)(PPh₃)₄]⁺ can be activated towards further alkylation. Dialkylated complexes [Pt₂(µ-SR)₂(P–P)₂]²⁺ (P–P = 2 × PPh₃, Ph₂P(CH₂)₃PPh₂) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4′-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph₂P(CH₂)₃PPh₂ or dppp] which enhances the nucleophilicity of the {Pt₂(µ-S)₂} core. This strategy led to the activation of [Pt₂(µ-S)(µ-SR)(PPh₃)₄]⁺ towards R–X as well as isolation and crystallographic elucidation of [Pt₂(µ-SC₁₀H₁₀N)₂(PPh₃)₄](PF₆)₂ (2a), [Pt₂(µ-SCH₂C(O)C₆H₄C₆H₅)₂(PPh₃)₄](PF₆)₂ (2b), and a range of functionalized-thiolato bridged complexes such as [Pt₂(µ-SR)₂(dppp)₂](PF₆)₂ [R = –CH₂C₆H₅ (8a), –CH₂CHCH₂ (8b) and –CH₂CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt₂(µ-S)₂(P–P)₂], thereby guiding the bench-top synthesis of some products observed spectroscopically.

Original language	English
Pages (from-to)	4008-4016
Journal	Dalton Transactions
Issue number	36
DOIs	https://doi.org/10.1039/b707526j
Publication status	Published - 2 Aug 2007

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@article{04d83afe00184fb99a9557bcc8cf44b8,

title = "Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]",

abstract = "The normally robust monoalkylated complexes [Pt2(µ-S)(µ-SR)(PPh3)4]+ can be activated towards further alkylation. Dialkylated complexes [Pt2(µ-SR)2(P–P)2]2+ (P–P = 2 × PPh3, Ph2P(CH2)3PPh2) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4′-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph2P(CH2)3PPh2 or dppp] which enhances the nucleophilicity of the \{Pt2(µ-S)2\} core. This strategy led to the activation of [Pt2(µ-S)(µ-SR)(PPh3)4]+ towards R–X as well as isolation and crystallographic elucidation of [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a), [Pt2(µ-SCH2C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b), and a range of functionalized-thiolato bridged complexes such as [Pt2(µ-SR)2(dppp)2](PF6)2 [R = –CH2C6H5 (8a), –CH2CHCH2 (8b) and –CH2CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt2(µ-S)2(P–P)2], thereby guiding the bench-top synthesis of some products observed spectroscopically.",

author = "Chong, \{Siew Huay\} and William Henderson and Hor, \{T S Andy\}",

year = "2007",

month = aug,

day = "2",

doi = "10.1039/b707526j",

language = "English",

pages = "4008--4016",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "36",

}

TY - JOUR

T1 - Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]

AU - Chong, Siew Huay

AU - Henderson, William

AU - Hor, T S Andy

PY - 2007/8/2

Y1 - 2007/8/2

N2 - The normally robust monoalkylated complexes [Pt2(µ-S)(µ-SR)(PPh3)4]+ can be activated towards further alkylation. Dialkylated complexes [Pt2(µ-SR)2(P–P)2]2+ (P–P = 2 × PPh3, Ph2P(CH2)3PPh2) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4′-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph2P(CH2)3PPh2 or dppp] which enhances the nucleophilicity of the {Pt2(µ-S)2} core. This strategy led to the activation of [Pt2(µ-S)(µ-SR)(PPh3)4]+ towards R–X as well as isolation and crystallographic elucidation of [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a), [Pt2(µ-SCH2C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b), and a range of functionalized-thiolato bridged complexes such as [Pt2(µ-SR)2(dppp)2](PF6)2 [R = –CH2C6H5 (8a), –CH2CHCH2 (8b) and –CH2CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt2(µ-S)2(P–P)2], thereby guiding the bench-top synthesis of some products observed spectroscopically.

AB - The normally robust monoalkylated complexes [Pt2(µ-S)(µ-SR)(PPh3)4]+ can be activated towards further alkylation. Dialkylated complexes [Pt2(µ-SR)2(P–P)2]2+ (P–P = 2 × PPh3, Ph2P(CH2)3PPh2) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4′-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph2P(CH2)3PPh2 or dppp] which enhances the nucleophilicity of the {Pt2(µ-S)2} core. This strategy led to the activation of [Pt2(µ-S)(µ-SR)(PPh3)4]+ towards R–X as well as isolation and crystallographic elucidation of [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a), [Pt2(µ-SCH2C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b), and a range of functionalized-thiolato bridged complexes such as [Pt2(µ-SR)2(dppp)2](PF6)2 [R = –CH2C6H5 (8a), –CH2CHCH2 (8b) and –CH2CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt2(µ-S)2(P–P)2], thereby guiding the bench-top synthesis of some products observed spectroscopically.

U2 - 10.1039/b707526j

DO - 10.1039/b707526j

M3 - Article

SN - 1477-9226

SP - 4008

EP - 4016

JO - Dalton Transactions

JF - Dalton Transactions

IS - 36

ER -

Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]

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