Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

Piotr Wawrzyniak; Amy Fuller; Alexandra Martha Zoya Slawin; Petr Kilian

doi:10.1021/ic801833a

Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

Piotr Wawrzyniak, Amy Fuller, Alexandra Martha Zoya Slawin, Petr Kilian

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

Abstract

The reaction of 5-diphenoxyphosphanyl-6-diisopropylphosphinoacenaphthene 12 with chlorotrimethylsilane unexpectedly gave a phosphonium-phosphine compound 13, containing the structural motif of four phosphorus atoms connected in a chain. To explain the mechanism of this complex transformation, a proposed intermediate 5-dichlorophosphino-6-diisopropylphosphinoacenaphthene 14 was synthesized by an alternative method. The two (formally) phosphine environments in 14 form an intramolecular donor-acceptor (phosphonium-phosphoranide) complex, stable at room temperature in the solid state and as a solution in certain solvents. A P-31 NMR mechanistic study showed that, despite the presence of a rigid acenaphthene backbone, 14 is unstable in the presence of nucleophiles and disproportionates into 13 and other phosphorus containing products. Both 13 and 14 have been crystallographically characterized.

Original language	English
Pages (from-to)	2500-2506
Number of pages	7
Journal	Inorganic Chemistry
Volume	48
Issue number	6
DOIs	https://doi.org/10.1021/ic801833a
Publication status	Published - 16 Mar 2009

Keywords

PHOSPHORUS
CHLORIDES
SKELETON
ELEMENTS
SYSTEM
CATION

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10.1021/ic801833a

Cite this

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title = "Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes",

abstract = "The reaction of 5-diphenoxyphosphanyl-6-diisopropylphosphinoacenaphthene 12 with chlorotrimethylsilane unexpectedly gave a phosphonium-phosphine compound 13, containing the structural motif of four phosphorus atoms connected in a chain. To explain the mechanism of this complex transformation, a proposed intermediate 5-dichlorophosphino-6-diisopropylphosphinoacenaphthene 14 was synthesized by an alternative method. The two (formally) phosphine environments in 14 form an intramolecular donor-acceptor (phosphonium-phosphoranide) complex, stable at room temperature in the solid state and as a solution in certain solvents. A P-31 NMR mechanistic study showed that, despite the presence of a rigid acenaphthene backbone, 14 is unstable in the presence of nucleophiles and disproportionates into 13 and other phosphorus containing products. Both 13 and 14 have been crystallographically characterized.",

keywords = "PHOSPHORUS, CHLORIDES, SKELETON, ELEMENTS, SYSTEM, CATION",

author = "Piotr Wawrzyniak and Amy Fuller and Slawin, \{Alexandra Martha Zoya\} and Petr Kilian",

year = "2009",

month = mar,

day = "16",

doi = "10.1021/ic801833a",

language = "English",

volume = "48",

pages = "2500--2506",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

number = "6",

}

TY - JOUR

T1 - Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

AU - Wawrzyniak, Piotr

AU - Fuller, Amy

AU - Slawin, Alexandra Martha Zoya

AU - Kilian, Petr

PY - 2009/3/16

Y1 - 2009/3/16

N2 - The reaction of 5-diphenoxyphosphanyl-6-diisopropylphosphinoacenaphthene 12 with chlorotrimethylsilane unexpectedly gave a phosphonium-phosphine compound 13, containing the structural motif of four phosphorus atoms connected in a chain. To explain the mechanism of this complex transformation, a proposed intermediate 5-dichlorophosphino-6-diisopropylphosphinoacenaphthene 14 was synthesized by an alternative method. The two (formally) phosphine environments in 14 form an intramolecular donor-acceptor (phosphonium-phosphoranide) complex, stable at room temperature in the solid state and as a solution in certain solvents. A P-31 NMR mechanistic study showed that, despite the presence of a rigid acenaphthene backbone, 14 is unstable in the presence of nucleophiles and disproportionates into 13 and other phosphorus containing products. Both 13 and 14 have been crystallographically characterized.

AB - The reaction of 5-diphenoxyphosphanyl-6-diisopropylphosphinoacenaphthene 12 with chlorotrimethylsilane unexpectedly gave a phosphonium-phosphine compound 13, containing the structural motif of four phosphorus atoms connected in a chain. To explain the mechanism of this complex transformation, a proposed intermediate 5-dichlorophosphino-6-diisopropylphosphinoacenaphthene 14 was synthesized by an alternative method. The two (formally) phosphine environments in 14 form an intramolecular donor-acceptor (phosphonium-phosphoranide) complex, stable at room temperature in the solid state and as a solution in certain solvents. A P-31 NMR mechanistic study showed that, despite the presence of a rigid acenaphthene backbone, 14 is unstable in the presence of nucleophiles and disproportionates into 13 and other phosphorus containing products. Both 13 and 14 have been crystallographically characterized.

KW - PHOSPHORUS

KW - CHLORIDES

KW - SKELETON

KW - ELEMENTS

KW - SYSTEM

KW - CATION

UR - https://www.scopus.com/pages/publications/64349100822

U2 - 10.1021/ic801833a

DO - 10.1021/ic801833a

M3 - Article

SN - 0020-1669

VL - 48

SP - 2500

EP - 2506

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 6

ER -

Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

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Keywords

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EP/E010395/1 STABLE PHOSPHORUS CENTRED: Stable Phosphorous Cenred Radicals and Odd Electron Bonds

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Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

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EP/E010395/1 STABLE PHOSPHORUS CENTRED: Stable Phosphorous Cenred Radicals and Odd Electron Bonds

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