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New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry

New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry
New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry
The new ligands dihydrobis[3-(4-pyridyl)pyrazol-1-yl]borate [Bp(4py)](-), hydrotris[3-(4-pyridyl)pyrazol-1-yl]borate [Tp(4py)](-), tetrakis[3-(4-pyridyl)pyrazol-1-yl]borate [Tkp(3py)](-), dihydrobis[3-(3-pyridyl)pyrazol-1-yl]borate [Bp(3py)](-), hydrotris[3-(3-pyridyl)pyrazol-1-yl]borate [Tp(3py)](-) and tetrakis[3-(3-pyridyl)pyrazol-1-yl]borate [Tkp(4py)](-) are derivatives of the well known bis-, tris- and tetrakis-(pyrazolyl)borate cores, bearing 4-pyridyl or 3-pyridyl substituents attached to the pyrazolyl C-3 positions. These pyridyl groups cannot chelate to the metal ions in the poly(pyrazolyl) cavity but are externally directed. Structural studies on a range of metal complexes show how, in many cases, coordination of these pendant pyridyl groups to the M(pyrazolyl), core of an adjacent metal complex fragment results in formation of coordination oligomers or polymeric networks. [Tl(B-3py)], [TlBp4y] and [Tl(Tp(4py))] form one-dimensional polymeric chains via coordination of one of their pendant pyridyl units to the Tl(I) centre of an adjacent complex fragment; in contrast, in [Tl(Tp(3py))] coordination of all three pendant pyridyl units to separate Tl(I) neighbours results in formation of a two-dimensional polymeric sheet. In [Tl(Tkp(3py))] and [Tl(Tkp(4py))] the Tl(I) is coordinated by two or three of the four pyrazolyl arms, respectively; bridging interactions of pendant 4-pyridyl groups with adjacent Tl(I) centres result in a two-dimensional sheet forming in each case. In Ag(Tkp(4py)) each Ag(I) ion is coordinated by two pyrazolyl rings, and two bridging pyridyl ligands from other complex units, resulting in a one-dimensional chain consisting of pairs of cross-linked zigzag chains. In contrast to these polymeric coordination networks, the structures of [Cu(Tp(4py))] and [(Tp(3py))Cd(CH3CO2)] are dimers, with a pendant pyridyl residue from the first metal centre attaching to a vacant coordination site on the second, and vice versa; these dimers are stabilised by pi-stacking interactions between sections of the two ligands. [Ni(Tp(3py)),] is monomeric, with an octahedral coordination geometry arising from two tris(pyrazolyl)borate chelates; the array of pendant 3-pyridyl groups is involved only in intramolecular hydrogen-bonding. [(Tp(4pY))Re(CO)(3)] is also monomeric, with a facial arrangement of three pyrazolyl ligands and three carbonyls, with the pendant 4-pyridyl groups not further coordinated. [(Tp(2py))Re(CO)(3)], based on the related ligand hydrotris[3-(2-pyridyl)pyrazol-1-yl]borate, has a similar fac-(CO)(3)(pyrazolyl)(2) coordination geometry.
crystal-structures, carbonyl-complexes, metal-ions, thallium(i), derivatives, mononuclear
1477-9226
1910-1923
Adams, Harry
4379cc0a-3ba1-4b32-aa76-14f557e5c010
Batten, Stuart R.
52b2fd45-5e56-4820-a239-a6ac7cf3144b
Davies, Graham M.
c6ac1fc9-fd58-4dfd-ae15-fc813b1dc243
Duriska, Martin B.
f0e49b6c-dc25-434c-b934-6311b2f6cb6e
Jeffery, John C.
796d502d-af4e-445f-ae1f-b8e50aa65b81
Jensen, Paul
1cfc9b74-1018-4848-9a94-b49afb907651
Lu, Jinzhen
97f2d57b-64f9-44c3-bc80-b7b739d8d278
Motson, Graham R.
bdc936c6-9cc8-4640-9070-fbf7ead9f804
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Ward, Michael D.
da487000-9f37-440b-a952-e09671f28e3b
Adams, Harry
4379cc0a-3ba1-4b32-aa76-14f557e5c010
Batten, Stuart R.
52b2fd45-5e56-4820-a239-a6ac7cf3144b
Davies, Graham M.
c6ac1fc9-fd58-4dfd-ae15-fc813b1dc243
Duriska, Martin B.
f0e49b6c-dc25-434c-b934-6311b2f6cb6e
Jeffery, John C.
796d502d-af4e-445f-ae1f-b8e50aa65b81
Jensen, Paul
1cfc9b74-1018-4848-9a94-b49afb907651
Lu, Jinzhen
97f2d57b-64f9-44c3-bc80-b7b739d8d278
Motson, Graham R.
bdc936c6-9cc8-4640-9070-fbf7ead9f804
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Ward, Michael D.
da487000-9f37-440b-a952-e09671f28e3b

Adams, Harry, Batten, Stuart R., Davies, Graham M., Duriska, Martin B., Jeffery, John C., Jensen, Paul, Lu, Jinzhen, Motson, Graham R., Coles, Simon J., Hursthouse, Michael B. and Ward, Michael D. (2005) New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry. Dalton Transactions, (11), 1910-1923. (doi:10.1039/b502892b).

Record type: Article

Abstract

The new ligands dihydrobis[3-(4-pyridyl)pyrazol-1-yl]borate [Bp(4py)](-), hydrotris[3-(4-pyridyl)pyrazol-1-yl]borate [Tp(4py)](-), tetrakis[3-(4-pyridyl)pyrazol-1-yl]borate [Tkp(3py)](-), dihydrobis[3-(3-pyridyl)pyrazol-1-yl]borate [Bp(3py)](-), hydrotris[3-(3-pyridyl)pyrazol-1-yl]borate [Tp(3py)](-) and tetrakis[3-(3-pyridyl)pyrazol-1-yl]borate [Tkp(4py)](-) are derivatives of the well known bis-, tris- and tetrakis-(pyrazolyl)borate cores, bearing 4-pyridyl or 3-pyridyl substituents attached to the pyrazolyl C-3 positions. These pyridyl groups cannot chelate to the metal ions in the poly(pyrazolyl) cavity but are externally directed. Structural studies on a range of metal complexes show how, in many cases, coordination of these pendant pyridyl groups to the M(pyrazolyl), core of an adjacent metal complex fragment results in formation of coordination oligomers or polymeric networks. [Tl(B-3py)], [TlBp4y] and [Tl(Tp(4py))] form one-dimensional polymeric chains via coordination of one of their pendant pyridyl units to the Tl(I) centre of an adjacent complex fragment; in contrast, in [Tl(Tp(3py))] coordination of all three pendant pyridyl units to separate Tl(I) neighbours results in formation of a two-dimensional polymeric sheet. In [Tl(Tkp(3py))] and [Tl(Tkp(4py))] the Tl(I) is coordinated by two or three of the four pyrazolyl arms, respectively; bridging interactions of pendant 4-pyridyl groups with adjacent Tl(I) centres result in a two-dimensional sheet forming in each case. In Ag(Tkp(4py)) each Ag(I) ion is coordinated by two pyrazolyl rings, and two bridging pyridyl ligands from other complex units, resulting in a one-dimensional chain consisting of pairs of cross-linked zigzag chains. In contrast to these polymeric coordination networks, the structures of [Cu(Tp(4py))] and [(Tp(3py))Cd(CH3CO2)] are dimers, with a pendant pyridyl residue from the first metal centre attaching to a vacant coordination site on the second, and vice versa; these dimers are stabilised by pi-stacking interactions between sections of the two ligands. [Ni(Tp(3py)),] is monomeric, with an octahedral coordination geometry arising from two tris(pyrazolyl)borate chelates; the array of pendant 3-pyridyl groups is involved only in intramolecular hydrogen-bonding. [(Tp(4pY))Re(CO)(3)] is also monomeric, with a facial arrangement of three pyrazolyl ligands and three carbonyls, with the pendant 4-pyridyl groups not further coordinated. [(Tp(2py))Re(CO)(3)], based on the related ligand hydrotris[3-(2-pyridyl)pyrazol-1-yl]borate, has a similar fac-(CO)(3)(pyrazolyl)(2) coordination geometry.

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Published date: 7 June 2005
Keywords: crystal-structures, carbonyl-complexes, metal-ions, thallium(i), derivatives, mononuclear

Identifiers

Local EPrints ID: 20698
URI: http://eprints.soton.ac.uk/id/eprint/20698
ISSN: 1477-9226
PURE UUID: 1441a738-5051-4baf-9dff-caa302ea2397
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 28 Feb 2006
Last modified: 29 Oct 2019 01:58

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Contributors

Author: Harry Adams
Author: Stuart R. Batten
Author: Graham M. Davies
Author: Martin B. Duriska
Author: John C. Jeffery
Author: Paul Jensen
Author: Jinzhen Lu
Author: Graham R. Motson
Author: Simon J. Coles ORCID iD
Author: Michael D. Ward

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