Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo)
In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<sub>3<...
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MDPI AG
2022-05-01
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| Online Access: | https://www.mdpi.com/2304-6740/10/6/75 |
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| author | Sourav Mondal Wei-Xing Chen Zhong-Ming Sun John E. McGrady |
| author_facet | Sourav Mondal Wei-Xing Chen Zhong-Ming Sun John E. McGrady |
| author_sort | Sourav Mondal |
| collection | DOAJ |
| description | In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup>, both of which have a pentagonal bipyramidal core. The structures are similar to that of previously reported [(CO)<sub>3</sub>MoPb<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup> and our analysis of the bonding suggests that they are best formulated as containing Sn<sub>5</sub><sup>4−</sup> rings bridging two zerovalent M(CO)<sub>3</sub> fragments. The electronic structure is compared to two isolobal M<sub>2</sub>E<sub>5</sub> clusters, [CpCrP<sub>5</sub>CrCp]<sup>−</sup> and Tl<sub>7</sub><sup>7−</sup>, both of which show clear evidence for <i>trans</i>-annular bonds between the apical atoms that is not immediately obvious in the title clusters. Our analysis shows that the balance between E-E and M-M bonding is a delicate one, and shifts in the relative energies of the orbitals on the E<sub>5</sub> and M<sub>2</sub> fragments generate a continuum of bonding situations linked by the degree of localisation of the cluster LUMO. |
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| last_indexed | 2024-03-09T23:30:12Z |
| publishDate | 2022-05-01 |
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| series | Inorganics |
| spelling | doaj.art-672f66d6f43c47feac7e5c92fe6330812023-11-23T17:10:28ZengMDPI AGInorganics2304-67402022-05-011067510.3390/inorganics10060075Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo)Sourav Mondal0Wei-Xing Chen1Zhong-Ming Sun2John E. McGrady3Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UKState Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin 300350, ChinaState Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin 300350, ChinaDepartment of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UKIn this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup>, both of which have a pentagonal bipyramidal core. The structures are similar to that of previously reported [(CO)<sub>3</sub>MoPb<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup> and our analysis of the bonding suggests that they are best formulated as containing Sn<sub>5</sub><sup>4−</sup> rings bridging two zerovalent M(CO)<sub>3</sub> fragments. The electronic structure is compared to two isolobal M<sub>2</sub>E<sub>5</sub> clusters, [CpCrP<sub>5</sub>CrCp]<sup>−</sup> and Tl<sub>7</sub><sup>7−</sup>, both of which show clear evidence for <i>trans</i>-annular bonds between the apical atoms that is not immediately obvious in the title clusters. Our analysis shows that the balance between E-E and M-M bonding is a delicate one, and shifts in the relative energies of the orbitals on the E<sub>5</sub> and M<sub>2</sub> fragments generate a continuum of bonding situations linked by the degree of localisation of the cluster LUMO.https://www.mdpi.com/2304-6740/10/6/75Zintl clustersX-ray crystallographyDensity Functional Theory |
| spellingShingle | Sourav Mondal Wei-Xing Chen Zhong-Ming Sun John E. McGrady Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) Inorganics Zintl clusters X-ray crystallography Density Functional Theory |
| title | Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) |
| title_full | Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) |
| title_fullStr | Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) |
| title_full_unstemmed | Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) |
| title_short | Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a <i>cyclo</i>-Sn<sub>5</sub> Ring, [(CO)<sub>3</sub>MSn<sub>5</sub>M(CO)<sub>3</sub>]<sup>4−</sup> (M = Cr, Mo) |
| title_sort | synthesis structure and bonding in pentagonal bipyramidal cluster compounds containing a i cyclo i sn sub 5 sub ring co sub 3 sub msn sub 5 sub m co sub 3 sub sup 4 sup m cr mo |
| topic | Zintl clusters X-ray crystallography Density Functional Theory |
| url | https://www.mdpi.com/2304-6740/10/6/75 |
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