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Isomeric dinuclear gold(I) complexes with highly functionalised ditertiary phosphines: self-assembly of dimers, rings and 1-D polymeric chains

Isomeric dinuclear gold(I) complexes with highly functionalised ditertiary phosphines: self-assembly of dimers, rings and 1-D polymeric chains
Isomeric dinuclear gold(I) complexes with highly functionalised ditertiary phosphines: self-assembly of dimers, rings and 1-D polymeric chains
An isomeric series of six linear, dinuclear, gold(I) complexes (AuCl)(2){P, P-C6H4N( CH2PPh2)(2)(CO2H)(OH)} 6a - 6f have been synthesised in high yields (> 90%) from AuCl(tht) (tht = tetrahydrothiophene) and the appropriate building blocks C6H4N(CH2PPh2)(2)(CO2H)(OH) 3a - 3f in CH2Cl2. The diphosphine ligands C6H4N(CH2PPh2)(2) 1, 4-CO2HC6H4N(CH2PPh2)(2) 2 and their corresponding digold(I) complexes 4 and 5 have also been prepared. Solution NMR (P-31{H-1}, H-1), FT-IR and microanalytical data are in full agreement with the proposed structures. Single crystal X-ray studies confirm that in each case, compounds 4, 5, 6a - 6e are linear, with typical Au - P [2.227(4) - 2.2349(17) angstrom]/Au - Cl [2.271(2) - 2.325( 4) angstrom] bond lengths and P - Au - Cl [169.37(1) - 179.05(4)degrees] bond angles. Furthermore these studies demonstrate the relationship between regioselectivity, with respect to the -N(CH2PPh2)(2), -CO2H and -OH functionalities around the benzene core, and solid state structures of the gold(I) complexes 6a - 6e. In 6a, molecules are associated into pairs through classical intermolecular O - (HO)-O-••• hydrogen bonding, whilst in 6b and 6c, dimer pairs are formed using intermolecular O - (HCl)-Cl-••• hydrogen bonds. 1- D chains of alternate 20-/22- or 8-/18-membered hydrogen bonded rings are propagated using O - (HCl)-Cl-••• and/or O - (HO)-O-••• hydrogen bonds in compounds 6d and 6e. The Au. Au separation decreases from 6.179(3) Å (for 6a) to 3.0722(9) Å (for 6e) suggesting that aurophilicity increases within this series. The X-ray structure of a representative diphosphine 3a is also presented.
graph-set analysis, condensation-reactions, coordination polymers, tertiary phosphines, hydrogen, aurophilicity, chemistry, ligands, acid, 1, 3, 5-triaza-7-phosphaadamantane
1466-8033
140-149
Smith, Martin B.
bc6e6c8e-8c15-44a8-84fa-2fe923ba21f8
Dale, Sophie H.
3b14c536-c5d6-4e3d-8af9-e0245c4c0fef
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, Michael B.
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Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Smith, Martin B.
bc6e6c8e-8c15-44a8-84fa-2fe923ba21f8
Dale, Sophie H.
3b14c536-c5d6-4e3d-8af9-e0245c4c0fef
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161

Smith, Martin B., Dale, Sophie H., Coles, Simon J., Gelbrich, Thomas, Hursthouse, Michael B. and Light, Mark E. (2006) Isomeric dinuclear gold(I) complexes with highly functionalised ditertiary phosphines: self-assembly of dimers, rings and 1-D polymeric chains. CrystEngComm, 8 (2), 140-149. (doi:10.1039/b516023e).

Record type: Article

Abstract

An isomeric series of six linear, dinuclear, gold(I) complexes (AuCl)(2){P, P-C6H4N( CH2PPh2)(2)(CO2H)(OH)} 6a - 6f have been synthesised in high yields (> 90%) from AuCl(tht) (tht = tetrahydrothiophene) and the appropriate building blocks C6H4N(CH2PPh2)(2)(CO2H)(OH) 3a - 3f in CH2Cl2. The diphosphine ligands C6H4N(CH2PPh2)(2) 1, 4-CO2HC6H4N(CH2PPh2)(2) 2 and their corresponding digold(I) complexes 4 and 5 have also been prepared. Solution NMR (P-31{H-1}, H-1), FT-IR and microanalytical data are in full agreement with the proposed structures. Single crystal X-ray studies confirm that in each case, compounds 4, 5, 6a - 6e are linear, with typical Au - P [2.227(4) - 2.2349(17) angstrom]/Au - Cl [2.271(2) - 2.325( 4) angstrom] bond lengths and P - Au - Cl [169.37(1) - 179.05(4)degrees] bond angles. Furthermore these studies demonstrate the relationship between regioselectivity, with respect to the -N(CH2PPh2)(2), -CO2H and -OH functionalities around the benzene core, and solid state structures of the gold(I) complexes 6a - 6e. In 6a, molecules are associated into pairs through classical intermolecular O - (HO)-O-••• hydrogen bonding, whilst in 6b and 6c, dimer pairs are formed using intermolecular O - (HCl)-Cl-••• hydrogen bonds. 1- D chains of alternate 20-/22- or 8-/18-membered hydrogen bonded rings are propagated using O - (HCl)-Cl-••• and/or O - (HO)-O-••• hydrogen bonds in compounds 6d and 6e. The Au. Au separation decreases from 6.179(3) Å (for 6a) to 3.0722(9) Å (for 6e) suggesting that aurophilicity increases within this series. The X-ray structure of a representative diphosphine 3a is also presented.

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More information

Published date: 2006
Keywords: graph-set analysis, condensation-reactions, coordination polymers, tertiary phosphines, hydrogen, aurophilicity, chemistry, ligands, acid, 1, 3, 5-triaza-7-phosphaadamantane

Identifiers

Local EPrints ID: 44549
URI: http://eprints.soton.ac.uk/id/eprint/44549
ISSN: 1466-8033
PURE UUID: 90e0cef2-87f1-4606-be44-a976f02b0796
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 05 Mar 2007
Last modified: 10 Dec 2019 01:51

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Contributors

Author: Martin B. Smith
Author: Sophie H. Dale
Author: Simon J. Coles ORCID iD
Author: Thomas Gelbrich
Author: Mark E. Light ORCID iD

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