Working towards the isolation of stable organometallic alkane complexes
Chapter 1 An introduction to the photochemistry of organometallic alkane and noble gas complexes, which have been the subject of this Thesis is outlined here. Time-resolved spectrometry and computational methods are also briefly described. Chapter 2 This Chapter looks at the photochemical reac...
| Main Author: | |
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
| Published: |
2024
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| Online Access: | https://eprints.nottingham.ac.uk/78083/ |
| _version_ | 1848801050565279744 |
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| author | Veasy, Agata |
| author_facet | Veasy, Agata |
| author_sort | Veasy, Agata |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Chapter 1
An introduction to the photochemistry of organometallic alkane and noble gas complexes, which have been the subject of this Thesis is outlined here. Time-resolved spectrometry and computational methods are also briefly described.
Chapter 2
This Chapter looks at the photochemical reactions of [Fe(CO)2(NO)2] in n-heptane, utilising time-resolved infrared spectroscopy (TRIR) with 266 nm excitation wavelength, spanning both nanosecond and picosecond timescales. On the nanosecond timescale, compelling evidence for the formation of [Fe(CO)(NO)2(heptane)] is presented. The alkane complex was found to decay with a lifetime of ca. 600-700 ns. The spectroscopic data confirming the formation of a secondary dimeric structure, [Fe2(CO)4(NO)3] in an eclipsed conformation, is also described here. The spectroscopic data obtained on the picosecond timescale is discussed. However, the formation of [Fe(CO)(NO)2(heptane)] was less evident here due to multiple overlapping species.
Chapter 3
A computational invesƟgaƟon of metal-alkane bond dissociation energies (BDEs) in cationic complexes, [CpM(CO)2(alkane)]+, where M = Fe, Ru and Os, and [CpM(CO (NO)(alkane)]+, where M = Mn or Re is described. Our findings highlighted several interesting trends in these complexes. The introduction of functional groups onto the cyclopentadienyl (Cp) ligand resulted in weaker metal-alkane interactions in both group 7 and group 8 complexes. Ruthenium alkane complexes were also found to have the lowest bond dissociation energies in all group 8 complexes, which deviates from reported trends.
[CpRe(CO)(NO)(cyclopentane)]+ was found to have the highest BDE of 110 kJ mol-1, which is a remarkable increase in comparison to its neutral analogue[CpRe(CO)2(cyclopentane)]. We have also synthesised a range of cationic precursor complexes as part of this Chapter.
Chapter 4
This Chapter delves into the investigation of the structural optimisation and metal-alkane bond dissociation energies (BDEs) using Density Functional Theory (DFT) in a series on group 5, 6, 7, 8, and 9 complexes, with a particular focus on the impact of nitrosyl ligand introduction on the strength of metal-alkane interaction. The introduction of the nitrosyl ligand generally strengthens the metal-alkane interaction, leading to higher BDE values across all investigated nitrosyl complexes, with increases ranging from 13 to 76 kJ mol-1. Trends seen in complexes within group 5 to 9 were identified. An equation was also derived to predict rate constants in CO-substitution of organometallic alkane complexes based on their calculated BDEs.
Chapter 5
A concise overview of the findings obtained in this Thesis is provided in this Chapter. Additionally, the summary of the implications of these findings for future directions is summarised here.
Chapter 6
An overview of the experimental methodologies, spectroscopic apparatus and analytical techniques employed throughout this Thesis is provided. |
| first_indexed | 2025-11-14T21:01:18Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-78083 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:01:18Z |
| publishDate | 2024 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-780832025-02-28T15:20:50Z https://eprints.nottingham.ac.uk/78083/ Working towards the isolation of stable organometallic alkane complexes Veasy, Agata Chapter 1 An introduction to the photochemistry of organometallic alkane and noble gas complexes, which have been the subject of this Thesis is outlined here. Time-resolved spectrometry and computational methods are also briefly described. Chapter 2 This Chapter looks at the photochemical reactions of [Fe(CO)2(NO)2] in n-heptane, utilising time-resolved infrared spectroscopy (TRIR) with 266 nm excitation wavelength, spanning both nanosecond and picosecond timescales. On the nanosecond timescale, compelling evidence for the formation of [Fe(CO)(NO)2(heptane)] is presented. The alkane complex was found to decay with a lifetime of ca. 600-700 ns. The spectroscopic data confirming the formation of a secondary dimeric structure, [Fe2(CO)4(NO)3] in an eclipsed conformation, is also described here. The spectroscopic data obtained on the picosecond timescale is discussed. However, the formation of [Fe(CO)(NO)2(heptane)] was less evident here due to multiple overlapping species. Chapter 3 A computational invesƟgaƟon of metal-alkane bond dissociation energies (BDEs) in cationic complexes, [CpM(CO)2(alkane)]+, where M = Fe, Ru and Os, and [CpM(CO (NO)(alkane)]+, where M = Mn or Re is described. Our findings highlighted several interesting trends in these complexes. The introduction of functional groups onto the cyclopentadienyl (Cp) ligand resulted in weaker metal-alkane interactions in both group 7 and group 8 complexes. Ruthenium alkane complexes were also found to have the lowest bond dissociation energies in all group 8 complexes, which deviates from reported trends. [CpRe(CO)(NO)(cyclopentane)]+ was found to have the highest BDE of 110 kJ mol-1, which is a remarkable increase in comparison to its neutral analogue[CpRe(CO)2(cyclopentane)]. We have also synthesised a range of cationic precursor complexes as part of this Chapter. Chapter 4 This Chapter delves into the investigation of the structural optimisation and metal-alkane bond dissociation energies (BDEs) using Density Functional Theory (DFT) in a series on group 5, 6, 7, 8, and 9 complexes, with a particular focus on the impact of nitrosyl ligand introduction on the strength of metal-alkane interaction. The introduction of the nitrosyl ligand generally strengthens the metal-alkane interaction, leading to higher BDE values across all investigated nitrosyl complexes, with increases ranging from 13 to 76 kJ mol-1. Trends seen in complexes within group 5 to 9 were identified. An equation was also derived to predict rate constants in CO-substitution of organometallic alkane complexes based on their calculated BDEs. Chapter 5 A concise overview of the findings obtained in this Thesis is provided in this Chapter. Additionally, the summary of the implications of these findings for future directions is summarised here. Chapter 6 An overview of the experimental methodologies, spectroscopic apparatus and analytical techniques employed throughout this Thesis is provided. 2024-07-24 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/78083/1/Veasy%2C%20Agata%20%5B14296812%5D%20Corrected%20PhD%20Thesis%20Submission.pdf Veasy, Agata (2024) Working towards the isolation of stable organometallic alkane complexes. PhD thesis, University of Nottingham. organometallic chemistry alkanes metal complexes synthesis |
| spellingShingle | organometallic chemistry alkanes metal complexes synthesis Veasy, Agata Working towards the isolation of stable organometallic alkane complexes |
| title | Working towards the isolation of stable organometallic alkane
complexes |
| title_full | Working towards the isolation of stable organometallic alkane
complexes |
| title_fullStr | Working towards the isolation of stable organometallic alkane
complexes |
| title_full_unstemmed | Working towards the isolation of stable organometallic alkane
complexes |
| title_short | Working towards the isolation of stable organometallic alkane
complexes |
| title_sort | working towards the isolation of stable organometallic alkane
complexes |
| topic | organometallic chemistry alkanes metal complexes synthesis |
| url | https://eprints.nottingham.ac.uk/78083/ |