Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters
Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3...
| Main Authors: | , , , , , , , , |
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| Format: | Journal Article |
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Elsevier
2015
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| Online Access: | http://hdl.handle.net/20.500.11937/6018 |
| _version_ | 1848744957417881600 |
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| author | Fu, J. Moxey, G. Morshedi, M. Barlow, A. Randles, M. Simpson, Peter Schwich, T. Cifuentes, M. Humphrey, M. |
| author_facet | Fu, J. Moxey, G. Morshedi, M. Barlow, A. Randles, M. Simpson, Peter Schwich, T. Cifuentes, M. Humphrey, M. |
| author_sort | Fu, J. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo–Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo–Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3–6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2–5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region. |
| first_indexed | 2025-11-14T06:09:43Z |
| format | Journal Article |
| id | curtin-20.500.11937-6018 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T06:09:43Z |
| publishDate | 2015 |
| publisher | Elsevier |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-60182017-09-13T14:39:53Z Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters Fu, J. Moxey, G. Morshedi, M. Barlow, A. Randles, M. Simpson, Peter Schwich, T. Cifuentes, M. Humphrey, M. Tetrahedral Mo2Ir2(μ3-CO)(μ-CO)5(CO)4(η5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(μ-CO)3(CO)6(L)(η5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC≡CSiPri3 proceeded by insertion into the Mo–Mo bond to give the pseudo-octahedral Mo2Ir2(μ4-η2-HC2SiPri3)(μ-CO)4(CO)4(η5-C5H5)2 (6) in fair yield. While MoIr3(μ-CO)3(CO)7(η5-C5H5) reacted with HC≡CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(μ-CO)3(CO)5(PPh3)2(η5-C5H5) reacted with the same alkyne via insertion into a Mo–Ir bond to afford the pseudo-octahedral MoIr3(μ4-η2-HC2SiMe3)(μ-CO)3(CO)4(PPh3)2(η5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(μ-CO)3(CO)6(PPh3)(η5-C5H5)2 (2), 3–6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2–5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region. 2015 Journal Article http://hdl.handle.net/20.500.11937/6018 10.1016/j.jorganchem.2015.09.034 Elsevier restricted |
| spellingShingle | Fu, J. Moxey, G. Morshedi, M. Barlow, A. Randles, M. Simpson, Peter Schwich, T. Cifuentes, M. Humphrey, M. Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title | Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title_full | Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title_fullStr | Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title_full_unstemmed | Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title_short | Mixed-metal cluster chemistry. 37. Syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| title_sort | mixed-metal cluster chemistry. 37. syntheses, structural, spectroscopic, electrochemical, and optical power limiting studies of tetranuclear molybdenum-iridium clusters |
| url | http://hdl.handle.net/20.500.11937/6018 |