Metal coordination to a dimetallaoctatetrayne

Andie R. Delaney; Benjamin J. Frogley; Anthony F. Hill

doi:10.1039/c9dt03041g

Metal coordination to a dimetallaoctatetrayne

Andie R. Delaney, Benjamin J. Frogley, Anthony F. Hill^*

^*Corresponding author for this work

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

15 Citations (Scopus)

Abstract

The reactions of the ditungstaoctatetrayne [(Tp∗)(CO)₂W(CCCCCC)W(CO)₂(Tp∗)] with several metal complexes have been investigated. Addition of [Co₂(CO)₈] occurs across the internal CC bonds, whereas [AuCl(SMe₂)] initially delivers 'AuCl' across the WC carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp∗)Cl₂W(CCCCCC)WCl₂(Tp∗)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR₃)] (R = Ph, Cy) in the presence of AgPF₆ prevents this oxidation and adds [AuPR₃]⁺ across the WC bonds to give dicationic derivatives. Finally, the reaction with [Pt(nbe)₃] (nbe = norbornene, bicyclo[2.2.1]hept-2-ene) and 1,5-cyclooctadiene (COD) adds a 'Pt(COD)' unit to one or both tungsten-carbon bonds, allowing both the mono- and diplatinum complexes to be isolated.

Original language	English
Pages (from-to)	13674-13684
Number of pages	11
Journal	Dalton Transactions
Volume	48
Issue number	36
DOIs	https://doi.org/10.1039/c9dt03041g
Publication status	Published - 2019

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title = "Metal coordination to a dimetallaoctatetrayne",

abstract = "The reactions of the ditungstaoctatetrayne [(Tp∗)(CO)2W(CCCCCC)W(CO)2(Tp∗)] with several metal complexes have been investigated. Addition of [Co2(CO)8] occurs across the internal CC bonds, whereas [AuCl(SMe2)] initially delivers 'AuCl' across the WC carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp∗)Cl2W(CCCCCC)WCl2(Tp∗)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR3)] (R = Ph, Cy) in the presence of AgPF6 prevents this oxidation and adds [AuPR3]+ across the WC bonds to give dicationic derivatives. Finally, the reaction with [Pt(nbe)3] (nbe = norbornene, bicyclo[2.2.1]hept-2-ene) and 1,5-cyclooctadiene (COD) adds a 'Pt(COD)' unit to one or both tungsten-carbon bonds, allowing both the mono- and diplatinum complexes to be isolated.",

author = "Delaney, {Andie R.} and Frogley, {Benjamin J.} and Hill, {Anthony F.}",

note = "Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9dt03041g",

language = "English",

volume = "48",

pages = "13674--13684",

journal = "Dalton Transactions",

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T1 - Metal coordination to a dimetallaoctatetrayne

AU - Delaney, Andie R.

AU - Frogley, Benjamin J.

AU - Hill, Anthony F.

PY - 2019

Y1 - 2019

N2 - The reactions of the ditungstaoctatetrayne [(Tp∗)(CO)2W(CCCCCC)W(CO)2(Tp∗)] with several metal complexes have been investigated. Addition of [Co2(CO)8] occurs across the internal CC bonds, whereas [AuCl(SMe2)] initially delivers 'AuCl' across the WC carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp∗)Cl2W(CCCCCC)WCl2(Tp∗)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR3)] (R = Ph, Cy) in the presence of AgPF6 prevents this oxidation and adds [AuPR3]+ across the WC bonds to give dicationic derivatives. Finally, the reaction with [Pt(nbe)3] (nbe = norbornene, bicyclo[2.2.1]hept-2-ene) and 1,5-cyclooctadiene (COD) adds a 'Pt(COD)' unit to one or both tungsten-carbon bonds, allowing both the mono- and diplatinum complexes to be isolated.

AB - The reactions of the ditungstaoctatetrayne [(Tp∗)(CO)2W(CCCCCC)W(CO)2(Tp∗)] with several metal complexes have been investigated. Addition of [Co2(CO)8] occurs across the internal CC bonds, whereas [AuCl(SMe2)] initially delivers 'AuCl' across the WC carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp∗)Cl2W(CCCCCC)WCl2(Tp∗)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR3)] (R = Ph, Cy) in the presence of AgPF6 prevents this oxidation and adds [AuPR3]+ across the WC bonds to give dicationic derivatives. Finally, the reaction with [Pt(nbe)3] (nbe = norbornene, bicyclo[2.2.1]hept-2-ene) and 1,5-cyclooctadiene (COD) adds a 'Pt(COD)' unit to one or both tungsten-carbon bonds, allowing both the mono- and diplatinum complexes to be isolated.

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U2 - 10.1039/c9dt03041g

DO - 10.1039/c9dt03041g

M3 - Article

SN - 1477-9226

VL - 48

SP - 13674

EP - 13684

JO - Dalton Transactions

JF - Dalton Transactions

IS - 36

ER -

Metal coordination to a dimetallaoctatetrayne

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