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Iron(ii) template synthesis of benzannulated triphospha- and triarsamacrocycles

Iron(ii) template synthesis of benzannulated triphospha- and triarsamacrocycles
Iron(ii) template synthesis of benzannulated triphospha- and triarsamacrocycles
Nine-membered 1,4,7-triphospha- and triarsamacrocycles with unsaturated benzo-backbones have been prepared using the [(CpFe)-Fe-R](+) unit as a template. The cyclisation involves the attack of a coordinated phosphide (or arsenide) nucleophile at an activated, electrophilic ortho-fluorophenyl substituent on a neighbouring pnictide donor. The macrocycle assembly is of the 2 + 1 type where two new chelate rings are formed from appropriately derivatised bidentate and monodentate phosphines/arsines. Both [(eta(5)-C5H5)Fe](+) and [(eta(5)-C5Me5)Fe](+) may be employed for the cyclisation with higher yields generally being observed with the unsubstituted Cp. All new compounds have been characterised by spectroscopic and analytical methods including the single-crystal X-ray structure determination of [(eta(5)-C5H5)Fe(tribenzo-9aneP(3)-Ph, Ph-2(F))](+), 3a, and [(eta(5)-C5H5)Fe(tribenzo-9aneAs(3)-Ph, Ph-2(F))](+), 5, as the tetraphenylborate salts. The crystal structures are isomorphous and show the unique conformation of these new macrocycles with a 'cup shaped' cavity formed by the rigid benzo-backbones. The 9aneAs(3) derivative is the first example of a nine-membered triarsamacrocycle.
0300-9246
9525-9532
Albers, Thomas
52b7ae0b-7556-48cc-9796-265de30dfa8e
Baker, Julia
f1d34178-f9bf-4c03-ba1a-147ebf3bb6a8
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Edwards, Peter G.
fcd5e923-9269-48a2-8fd3-0b8120f9a82b
Kariuki, Benson
1d259c49-3208-40d6-a351-e4a0fd681000
Newman, Paul D.
42e7ca00-b874-4cfb-a74a-6308015c4a8e
Albers, Thomas
52b7ae0b-7556-48cc-9796-265de30dfa8e
Baker, Julia
f1d34178-f9bf-4c03-ba1a-147ebf3bb6a8
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Edwards, Peter G.
fcd5e923-9269-48a2-8fd3-0b8120f9a82b
Kariuki, Benson
1d259c49-3208-40d6-a351-e4a0fd681000
Newman, Paul D.
42e7ca00-b874-4cfb-a74a-6308015c4a8e

Albers, Thomas, Baker, Julia, Coles, Simon J., Edwards, Peter G., Kariuki, Benson and Newman, Paul D. (2011) Iron(ii) template synthesis of benzannulated triphospha- and triarsamacrocycles. Dalton Transactions, 40 (37), 9525-9532. (doi:10.1039/c0dt01724h).

Record type: Article

Abstract

Nine-membered 1,4,7-triphospha- and triarsamacrocycles with unsaturated benzo-backbones have been prepared using the [(CpFe)-Fe-R](+) unit as a template. The cyclisation involves the attack of a coordinated phosphide (or arsenide) nucleophile at an activated, electrophilic ortho-fluorophenyl substituent on a neighbouring pnictide donor. The macrocycle assembly is of the 2 + 1 type where two new chelate rings are formed from appropriately derivatised bidentate and monodentate phosphines/arsines. Both [(eta(5)-C5H5)Fe](+) and [(eta(5)-C5Me5)Fe](+) may be employed for the cyclisation with higher yields generally being observed with the unsubstituted Cp. All new compounds have been characterised by spectroscopic and analytical methods including the single-crystal X-ray structure determination of [(eta(5)-C5H5)Fe(tribenzo-9aneP(3)-Ph, Ph-2(F))](+), 3a, and [(eta(5)-C5H5)Fe(tribenzo-9aneAs(3)-Ph, Ph-2(F))](+), 5, as the tetraphenylborate salts. The crystal structures are isomorphous and show the unique conformation of these new macrocycles with a 'cup shaped' cavity formed by the rigid benzo-backbones. The 9aneAs(3) derivative is the first example of a nine-membered triarsamacrocycle.

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More information

Published date: 2011
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 346132
URI: https://eprints.soton.ac.uk/id/eprint/346132
ISSN: 0300-9246
PURE UUID: 2ec17c60-6a60-4b45-a8b7-af13467d0319
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 19 Dec 2012 12:16
Last modified: 20 Jul 2019 01:09

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