A spectroscopic study of metal cluster bound C2-hydrocarbon ligands and the chemisorption of clusters onto oxide supports
A spectroscopic study of metal cluster bound C2-hydrocarbon ligands and the chemisorption of clusters onto oxide supports
Spectroscopic Studies were carried out to establish it and nmr parameters of metal cluster bound C -hydrocarbon ligands. A range of these ligands T1 2-ethylene, p2-n2-vinyl, U3-nz-vinylidene, nz-ethyne, U3-q2-ethyne,P3-nz-ethynyl and u3-n -ethylidyne bound to the same triosmium cluster framework were prepared and by comparison with diruthenium bound ligands u2-nz-vinyl, 112-TI 2-vinylidene, U2-nl-ethylidyne, 42-nl-methylcarbene, a u3-nl-ethylidyne triruthenium cluster and published data, the ability to identify particular coordinated ligands and the transferability of data between different metal centres was established. A detailed investigation of the reaction between [Ru3(CO)12] and ethylene was undertaken and a range of fluxional triruthenium complexes of the form [H2Ru3(CO)9(C2R2)] (R = H, Me, Et) together with triruthenium allyl complexes and a tetraruthenium butyne complex were identified using a combination of it, nmr and mass spectroscopies. The chemisorption from a solution of metal cluster carbonyls onto inorganic oxide supports was investigated and the resulting products identified by mixed 12C0/13C0 isotope studies with intensity and frequency matching to model complexes. The rhodium carbonyls [Rh6(C0)16] and [Rh4(CO)12] were found to undergo reversible formation of isolated Rh1(CO)z units and decarbonylation under mild conditions and metal aggregation under more forcing conditions. [Ru3(CO)12] was shown to interact with silica giving the decacarbonyl cluster [HRu3(CO110-O-SILICA], which decomposed to give oxidised species of the form [Ru1 (CO)2]n (n = 3 - 1). Pyrolysis and subsequent exposure to CO generated monocarbonyl species in +III and +IV oxidation states. The reaction with alumina and titania did not generate the initial supported cluster but similar oxidised dicarbonyl species were identified and for titania several monocarbonyl species were identified and the oxidation states +IV, +111 and 0 proposed. [0s3(CO)12] reacted with silica, alumina and titania giving [H0s3(C0)16-0-SURFACE] which was converted to a mixture of [0s11(C0)3]3 and [Os1F(CO)2]3 under pyrolysis conditions.
University of Southampton
McNulty, Gregory Stirling
1982
McNulty, Gregory Stirling
McNulty, Gregory Stirling
(1982)
A spectroscopic study of metal cluster bound C2-hydrocarbon ligands and the chemisorption of clusters onto oxide supports.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Spectroscopic Studies were carried out to establish it and nmr parameters of metal cluster bound C -hydrocarbon ligands. A range of these ligands T1 2-ethylene, p2-n2-vinyl, U3-nz-vinylidene, nz-ethyne, U3-q2-ethyne,P3-nz-ethynyl and u3-n -ethylidyne bound to the same triosmium cluster framework were prepared and by comparison with diruthenium bound ligands u2-nz-vinyl, 112-TI 2-vinylidene, U2-nl-ethylidyne, 42-nl-methylcarbene, a u3-nl-ethylidyne triruthenium cluster and published data, the ability to identify particular coordinated ligands and the transferability of data between different metal centres was established. A detailed investigation of the reaction between [Ru3(CO)12] and ethylene was undertaken and a range of fluxional triruthenium complexes of the form [H2Ru3(CO)9(C2R2)] (R = H, Me, Et) together with triruthenium allyl complexes and a tetraruthenium butyne complex were identified using a combination of it, nmr and mass spectroscopies. The chemisorption from a solution of metal cluster carbonyls onto inorganic oxide supports was investigated and the resulting products identified by mixed 12C0/13C0 isotope studies with intensity and frequency matching to model complexes. The rhodium carbonyls [Rh6(C0)16] and [Rh4(CO)12] were found to undergo reversible formation of isolated Rh1(CO)z units and decarbonylation under mild conditions and metal aggregation under more forcing conditions. [Ru3(CO)12] was shown to interact with silica giving the decacarbonyl cluster [HRu3(CO110-O-SILICA], which decomposed to give oxidised species of the form [Ru1 (CO)2]n (n = 3 - 1). Pyrolysis and subsequent exposure to CO generated monocarbonyl species in +III and +IV oxidation states. The reaction with alumina and titania did not generate the initial supported cluster but similar oxidised dicarbonyl species were identified and for titania several monocarbonyl species were identified and the oxidation states +IV, +111 and 0 proposed. [0s3(CO)12] reacted with silica, alumina and titania giving [H0s3(C0)16-0-SURFACE] which was converted to a mixture of [0s11(C0)3]3 and [Os1F(CO)2]3 under pyrolysis conditions.
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Published date: 1982
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Local EPrints ID: 460600
URI: http://eprints.soton.ac.uk/id/eprint/460600
PURE UUID: 58f6e595-d336-4335-962f-7dc90da4c38e
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Date deposited: 04 Jul 2022 18:25
Last modified: 04 Jul 2022 18:25
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Author:
Gregory Stirling McNulty
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