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Preparation and structures of coordination complexes of the very hard Lewis acids ZrF4 and HfF4

Preparation and structures of coordination complexes of the very hard Lewis acids ZrF4 and HfF4
Preparation and structures of coordination complexes of the very hard Lewis acids ZrF4 and HfF4
[MF4(dmso)2] (M = Zr or Hf) and [MF4(dmf)2], prepared by dissolving MF4·nH2O in the appropriate solvent, have been used as synthons for a range of complexes of these otherwise intractable tetrafluorides. These reagents react with OPR3 (R = Me or Ph) or OAsPh3 (L) in anhydrous CH2Cl2 to form six-coordinate [MF4L2] which exist as a mixture of cis (predominant form) and trans isomers in CH2Cl2 solution but which crystallise as trans (OPPh3, OAsPh3) or cis (OPMe3) forms. Cis-[ZrF4(OAsPh3)2] crystals were obtained from MeCN. Cis-[MF4(pyNO)2] and eight-coordinate (distorted dodecahedral) [MF4(L–L)2] (L–L = 2,2?-bipy, or 1,10-phen), and [MF4(Me4-cyclam)] were also obtained. Attempts to prepare complexes with the N-heterocyclic carbene, 1,3-(2,6-di-isopropylphenyl)imidazol-2-ylidene (IDiPP) or alkyl diphosphines were unsuccessful. Crystal structures are reported for trans-[ZrF4(OPPh3)2], cis- and trans-[ZrF4(OAsPh3)2], cis-[HfF4(OPMe3)2], [ZrF4(2,2?-bipy)2], cis-[HfF4(dmf)2], and geometric isomers (both pentagonal bipyramidal) of [(dmso)2F3M(?-F)2MF3(dmso)2]. The failed attempts to make IDiPP adducts led to crystals of [IDiPPH]3[M3F15] containing discrete anions based upon a triangle of M atoms with single F bridges. The results are compared with previous work on TiF4 adducts and with complexes of MCl4, and demonstrate that the MF4 are very hard Lewis acids, with a marked preference for O- over N-donors.
0300-9246
12548-12557
Benjamin, Sophie L.
3efd7555-c2e0-4330-a289-681bd13700df
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Benjamin, Sophie L.
3efd7555-c2e0-4330-a289-681bd13700df
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Pugh, David
9ec61267-ae4d-40d8-bebf-0d603e2588d3
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Benjamin, Sophie L., Levason, William, Pugh, David, Reid, Gillian and Zhang, Wenjian (2012) Preparation and structures of coordination complexes of the very hard Lewis acids ZrF4 and HfF4. Dalton Transactions, 41 (40), 12548-12557. (doi:10.1039/c2dt31501g).

Record type: Article

Abstract

[MF4(dmso)2] (M = Zr or Hf) and [MF4(dmf)2], prepared by dissolving MF4·nH2O in the appropriate solvent, have been used as synthons for a range of complexes of these otherwise intractable tetrafluorides. These reagents react with OPR3 (R = Me or Ph) or OAsPh3 (L) in anhydrous CH2Cl2 to form six-coordinate [MF4L2] which exist as a mixture of cis (predominant form) and trans isomers in CH2Cl2 solution but which crystallise as trans (OPPh3, OAsPh3) or cis (OPMe3) forms. Cis-[ZrF4(OAsPh3)2] crystals were obtained from MeCN. Cis-[MF4(pyNO)2] and eight-coordinate (distorted dodecahedral) [MF4(L–L)2] (L–L = 2,2?-bipy, or 1,10-phen), and [MF4(Me4-cyclam)] were also obtained. Attempts to prepare complexes with the N-heterocyclic carbene, 1,3-(2,6-di-isopropylphenyl)imidazol-2-ylidene (IDiPP) or alkyl diphosphines were unsuccessful. Crystal structures are reported for trans-[ZrF4(OPPh3)2], cis- and trans-[ZrF4(OAsPh3)2], cis-[HfF4(OPMe3)2], [ZrF4(2,2?-bipy)2], cis-[HfF4(dmf)2], and geometric isomers (both pentagonal bipyramidal) of [(dmso)2F3M(?-F)2MF3(dmso)2]. The failed attempts to make IDiPP adducts led to crystals of [IDiPPH]3[M3F15] containing discrete anions based upon a triangle of M atoms with single F bridges. The results are compared with previous work on TiF4 adducts and with complexes of MCl4, and demonstrate that the MF4 are very hard Lewis acids, with a marked preference for O- over N-donors.

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Published date: 2012
Organisations: Chemistry

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Local EPrints ID: 345340
URI: https://eprints.soton.ac.uk/id/eprint/345340
ISSN: 0300-9246
PURE UUID: f42d11aa-736c-43d9-acec-b0b22fe4e90b
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 20 Nov 2012 10:16
Last modified: 05 Nov 2019 02:09

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Contributors

Author: Sophie L. Benjamin
Author: William Levason ORCID iD
Author: David Pugh
Author: Gillian Reid ORCID iD
Author: Wenjian Zhang

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