Alkaline earth complexes of a sterically demanding guanidinate ligand
The synthesis of the guanidine MesN{C(NCy2)}N(H)Mes (LH; Mes = 2,4,6-Me3C6H2, Cy = cyclohexyl), and its use as a proligand for the synthesis of alkaline earth metal complexes are reported. Described herein are (i) an unusual Hauser base cubane, (ii) a homoleptic and a base-stabilized magnesium compl...
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Wiley
2015
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| Online Access: | https://eprints.nottingham.ac.uk/31238/ |
| _version_ | 1848794157211975680 |
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| author | Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. |
| author_facet | Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. |
| author_sort | Moxey, Graeme J. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The synthesis of the guanidine MesN{C(NCy2)}N(H)Mes (LH; Mes = 2,4,6-Me3C6H2, Cy = cyclohexyl), and its use as a proligand for the synthesis of alkaline earth metal complexes are reported. Described herein are (i) an unusual Hauser base cubane, (ii) a homoleptic and a base-stabilized magnesium complex featuring the same guanidinate ligands, and (iii) the comparison of a series of alkaline earth (Mg, Ca, Sr, Ba) bis(guanidinate) complexes, which allows the opportunity to compare the changing trends in bonding as the Group is descended. The reaction between LH and MeMgI(OEt2)2 yields the Hauser base as a mixture of the tetramer [Mg4L4(μ3-I)4] (1a) and dimer [Mg2L2(μ-I)2(OEt2)2] (1b), and the reaction with two equivalents of MgnBu2 leads to the formation of four-coordinate [MgL2] (2), which features a square-planar geometry for the magnesium cation, or five-coordinate [MgL2(THF)] (3), depending on the solvent used. 1a is the first crystallographically-characterized cubane structure to consist of four LAeX (L = ligand, X = halide) units. The complexes [AeL2(THF)2] (Ae = Ca, 4; Ae = Sr, 5) and [BaL2] (6) were synthesized via redox transmetallation/ligand exchange reactions. Complex 6 is the first example of a homoleptic, monomeric barium complex of the NCN ligand family, with the structure stabilized by a number of barium-arene interactions in the solid state. |
| first_indexed | 2025-11-14T19:11:44Z |
| format | Article |
| id | nottingham-31238 |
| institution | University of Nottingham Malaysia Campus |
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| last_indexed | 2025-11-14T19:11:44Z |
| publishDate | 2015 |
| publisher | Wiley |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-312382020-05-04T17:28:22Z https://eprints.nottingham.ac.uk/31238/ Alkaline earth complexes of a sterically demanding guanidinate ligand Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. The synthesis of the guanidine MesN{C(NCy2)}N(H)Mes (LH; Mes = 2,4,6-Me3C6H2, Cy = cyclohexyl), and its use as a proligand for the synthesis of alkaline earth metal complexes are reported. Described herein are (i) an unusual Hauser base cubane, (ii) a homoleptic and a base-stabilized magnesium complex featuring the same guanidinate ligands, and (iii) the comparison of a series of alkaline earth (Mg, Ca, Sr, Ba) bis(guanidinate) complexes, which allows the opportunity to compare the changing trends in bonding as the Group is descended. The reaction between LH and MeMgI(OEt2)2 yields the Hauser base as a mixture of the tetramer [Mg4L4(μ3-I)4] (1a) and dimer [Mg2L2(μ-I)2(OEt2)2] (1b), and the reaction with two equivalents of MgnBu2 leads to the formation of four-coordinate [MgL2] (2), which features a square-planar geometry for the magnesium cation, or five-coordinate [MgL2(THF)] (3), depending on the solvent used. 1a is the first crystallographically-characterized cubane structure to consist of four LAeX (L = ligand, X = halide) units. The complexes [AeL2(THF)2] (Ae = Ca, 4; Ae = Sr, 5) and [BaL2] (6) were synthesized via redox transmetallation/ligand exchange reactions. Complex 6 is the first example of a homoleptic, monomeric barium complex of the NCN ligand family, with the structure stabilized by a number of barium-arene interactions in the solid state. Wiley 2015-12-02 Article PeerReviewed Moxey, Graeme J., Blake, Alexander J., Lewis, William and Kays, Deborah L. (2015) Alkaline earth complexes of a sterically demanding guanidinate ligand. European Journal of Inorganic Chemistry, 2015 (36). pp. 5892-5902. ISSN 1434-1948 alkaline earth metals N ligands bidentate ligands ligand effects coordiination modes http://onlinelibrary.wiley.com/doi/10.1002/ejic.201501239/abstract doi:10.1002/ejic.201501239 doi:10.1002/ejic.201501239 |
| spellingShingle | alkaline earth metals N ligands bidentate ligands ligand effects coordiination modes Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title | Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title_full | Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title_fullStr | Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title_full_unstemmed | Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title_short | Alkaline earth complexes of a sterically demanding guanidinate ligand |
| title_sort | alkaline earth complexes of a sterically demanding guanidinate ligand |
| topic | alkaline earth metals N ligands bidentate ligands ligand effects coordiination modes |
| url | https://eprints.nottingham.ac.uk/31238/ https://eprints.nottingham.ac.uk/31238/ https://eprints.nottingham.ac.uk/31238/ |