{"id":{"repo_id":"auckland-ms","oai_identifier":"oai:researchspace.auckland.ac.nz:2292/2326"},"canonical_url":"https://search.dev.ndltd.org/etd/auckland-ms/oai:researchspace.auckland.ac.nz:2292/2326","repository":{"repo_id":"auckland-ms","name":"University of Auckland","base_url":"https://researchspace.auckland.ac.nz/server/oai/request"},"display":{"title":"Chemistry of low-valent osmium","abstract":"This study concerns the synthesis, structure and reactivity of complexes of d⁶ and d⁸ osmium. The reactivity of certain ligands coordinated to low-valent osmium has also been investigated. Various hydride complexes of osmium(II) were prepared as potential precursors of osmium(O). OsH₄(PPh₃)₃ reacts with p-tolylisocyanide (TIC) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (ETPO) to yield OsH₂(L)(PPh₃)₃ from which were derived OsH₂(L’)(L)(PPh₃)₂ (L, L’=CO, TIC, ETPO). Attempts to eliminate hydrogen from the dihydrides failed. OsHCl(CO) (PPh₃)₃ reacts with neutral ligands L (=TIC, ETPO, P(OMe)₃, P(OPh)₃, PPh₂Me) to give OsHCl(CO)(L)(PPh₃)₂ which, with silver perchlorate (L=TIC, ETPO only) afford OsH(OClO₃)(CO)(L)(PPh₃)₂. The labile perchlorate ligand can be replaced by ligands L’ affording [OsH(CO)(L)(L’)(PPh₃)₂]ClO4 (L=TIC, L’=CO, TIC, PPh₃ L=ETPO, L’=CO, ETPO). OsHCl(CO)(PPh₃)₃ reacts with silver perchlorate in acetonitrile to yield [OsH(CO)(CH𠠼N)₂(PPh₃)₂]ClO4, which in turn reacts with neutral ligands to give [OsH(CO)(CH₃N)(L)(PPh₃)₂]ClO₄ (L=CO, TIC, ETPO, PPh₃). Cationic [OsH(CO)₂(PPh₃)₃]+ and [OsH(TIC)₂(PPh₃)₃]+ can be prepared from the action of PPh₃ on [OsH(CO)₂(CH₃N)(PPh₃)₂]+ and TIC on OsH(O₂CCH₃)(PPh₃)₃ respectively. With base, [OsH(CO)(CH₃N)(PPh₃)₃]ClO4 affords OsH(OH)(CO)(PPh₃)₃ from which a series of hydroxide complexes OsH(OH)(CO)(L)(PPh₃)₂ (L=CO, TIC ETPO) can be obtained. The hydroxide group in OsH(OH)(CO)(PPh₃)₃ is cleaved by acids HX to yield OsHX(CO)(PPh₃)₃ (X=F, Br, Cl, I, CH₂, CF₂, SC₇H₇, OClO₃). Those members of the series with X=CN, N₃, OCN, SCN were obtained from OsH(OClO₃)(CO)(PPh₃)₃ and the appropriate anion. From the values of vCO for this series can be gained some understanding of the bonding properties of the anionic ligands.","abstract_html":"This study concerns the synthesis, structure and reactivity of complexes of d⁶ and d⁸ osmium. The reactivity of certain ligands coordinated to low-valent osmium has also been investigated. Various hydride complexes of osmium(II) were prepared as potential precursors of osmium(O). OsH₄(PPh₃)₃ reacts with p-tolylisocyanide (TIC) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (ETPO) to yield OsH₂(L)(PPh₃)₃ from which were derived OsH₂(L’)(L)(PPh₃)₂ (L, L’=CO, TIC, ETPO). Attempts to eliminate hydrogen from the dihydrides failed. OsHCl(CO) (PPh₃)₃ reacts with neutral ligands L (=TIC, ETPO, P(OMe)₃, P(OPh)₃, PPh₂Me) to give OsHCl(CO)(L)(PPh₃)₂ which, with silver perchlorate (L=TIC, ETPO only) afford OsH(OClO₃)(CO)(L)(PPh₃)₂. The labile perchlorate ligand can be replaced by ligands L’ affording [OsH(CO)(L)(L’)(PPh₃)₂]ClO4 (L=TIC, L’=CO, TIC, PPh₃ L=ETPO, L’=CO, ETPO). OsHCl(CO)(PPh₃)₃ reacts with silver perchlorate in acetonitrile to yield [OsH(CO)(CH𠠼N)₂(PPh₃)₂]ClO4, which in turn reacts with neutral ligands to give [OsH(CO)(CH₃N)(L)(PPh₃)₂]ClO₄ (L=CO, TIC, ETPO, PPh₃). Cationic [OsH(CO)₂(PPh₃)₃]+ and [OsH(TIC)₂(PPh₃)₃]+ can be prepared from the action of PPh₃ on [OsH(CO)₂(CH₃N)(PPh₃)₂]+ and TIC on OsH(O₂CCH₃)(PPh₃)₃ respectively. With base, [OsH(CO)(CH₃N)(PPh₃)₃]ClO4 affords OsH(OH)(CO)(PPh₃)₃ from which a series of hydroxide complexes OsH(OH)(CO)(L)(PPh₃)₂ (L=CO, TIC ETPO) can be obtained. The hydroxide group in OsH(OH)(CO)(PPh₃)₃ is cleaved by acids HX to yield OsHX(CO)(PPh₃)₃ (X=F, Br, Cl, I, CH₂, CF₂, SC₇H₇, OClO₃). Those members of the series with X=CN, N₃, OCN, SCN were obtained from OsH(OClO₃)(CO)(PPh₃)₃ and the appropriate anion. From the values of vCO for this series can be gained some understanding of the bonding properties of the anionic ligands.","abstract_has_math":false,"creators":["Grundy, Kevin Rodger"],"institution":"ResearchSpace@Auckland","degree_name":"PhD","degree_level":"Doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Associate Professor Warren Roper"],"committee_chairs":[],"committee_members":[],"year":1975,"date_issued":"1975","date_published":"1975","updated_at":"2026-07-24T01:06:10Z","subjects":[],"languages":["en"],"rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"rights_urls":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2292/2326","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Associate Professor Warren Roper"]},{"key":"dc:creator","label":"Author","values":["Grundy, Kevin Rodger"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2008-01-25T01:59:57Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2008-01-25T01:59:57Z"]},{"key":"dc:date.issued","label":"Date","values":["1975"]},{"key":"dc:publisher","label":"Institution","values":["ResearchSpace@Auckland"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["UoA217563"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["PhD"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["The University of Auckland"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/2292/2326"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This study concerns the synthesis, structure and reactivity of complexes of d⁶ and d⁸ osmium. The reactivity of certain ligands coordinated to low-valent osmium has also been investigated. Various hydride complexes of osmium(II) were prepared as potential precursors of osmium(O). OsH₄(PPh₃)₃ reacts with p-tolylisocyanide (TIC) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (ETPO) to yield OsH₂(L)(PPh₃)₃ from which were derived OsH₂(L’)(L)(PPh₃)₂ (L, L’=CO, TIC, ETPO). Attempts to eliminate hydrogen from the dihydrides failed. OsHCl(CO) (PPh₃)₃ reacts with neutral ligands L (=TIC, ETPO, P(OMe)₃, P(OPh)₃, PPh₂Me) to give OsHCl(CO)(L)(PPh₃)₂ which, with silver perchlorate (L=TIC, ETPO only) afford OsH(OClO₃)(CO)(L)(PPh₃)₂. The labile perchlorate ligand can be replaced by ligands L’ affording [OsH(CO)(L)(L’)(PPh₃)₂]ClO4 (L=TIC, L’=CO, TIC, PPh₃ L=ETPO, L’=CO, ETPO). OsHCl(CO)(PPh₃)₃ reacts with silver perchlorate in acetonitrile to yield [OsH(CO)(CH𠠼N)₂(PPh₃)₂]ClO4, which in turn reacts with neutral ligands to give [OsH(CO)(CH₃N)(L)(PPh₃)₂]ClO₄ (L=CO, TIC, ETPO, PPh₃). Cationic [OsH(CO)₂(PPh₃)₃]+ and [OsH(TIC)₂(PPh₃)₃]+ can be prepared from the action of PPh₃ on [OsH(CO)₂(CH₃N)(PPh₃)₂]+ and TIC on OsH(O₂CCH₃)(PPh₃)₃ respectively. With base, [OsH(CO)(CH₃N)(PPh₃)₃]ClO4 affords OsH(OH)(CO)(PPh₃)₃ from which a series of hydroxide complexes OsH(OH)(CO)(L)(PPh₃)₂ (L=CO, TIC ETPO) can be obtained. The hydroxide group in OsH(OH)(CO)(PPh₃)₃ is cleaved by acids HX to yield OsHX(CO)(PPh₃)₃ (X=F, Br, Cl, I, CH₂, CF₂, SC₇H₇, OClO₃). Those members of the series with X=CN, N₃, OCN, SCN were obtained from OsH(OClO₃)(CO)(PPh₃)₃ and the appropriate anion. From the values of vCO for this series can be gained some understanding of the bonding properties of the anionic ligands."]},{"key":"dc:format","label":"Dc Format","values":["Scanned from print thesis"]},{"key":"dc:title","label":"Title","values":["Chemistry of low-valent osmium"]}]}],"canonical_facts":{"dc:contributor.advisor":["Associate Professor Warren Roper"],"dc:creator":["Grundy, Kevin Rodger"],"dc:date.accessioned":["2008-01-25T01:59:57Z"],"dc:date.available":["2008-01-25T01:59:57Z"],"dc:date.issued":["1975"],"dc:description.abstract":["This study concerns the synthesis, structure and reactivity of complexes of d⁶ and d⁸ osmium. The reactivity of certain ligands coordinated to low-valent osmium has also been investigated. Various hydride complexes of osmium(II) were prepared as potential precursors of osmium(O). OsH₄(PPh₃)₃ reacts with p-tolylisocyanide (TIC) and 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (ETPO) to yield OsH₂(L)(PPh₃)₃ from which were derived OsH₂(L’)(L)(PPh₃)₂ (L, L’=CO, TIC, ETPO). Attempts to eliminate hydrogen from the dihydrides failed. OsHCl(CO) (PPh₃)₃ reacts with neutral ligands L (=TIC, ETPO, P(OMe)₃, P(OPh)₃, PPh₂Me) to give OsHCl(CO)(L)(PPh₃)₂ which, with silver perchlorate (L=TIC, ETPO only) afford OsH(OClO₃)(CO)(L)(PPh₃)₂. The labile perchlorate ligand can be replaced by ligands L’ affording [OsH(CO)(L)(L’)(PPh₃)₂]ClO4 (L=TIC, L’=CO, TIC, PPh₃ L=ETPO, L’=CO, ETPO). OsHCl(CO)(PPh₃)₃ reacts with silver perchlorate in acetonitrile to yield [OsH(CO)(CH𠠼N)₂(PPh₃)₂]ClO4, which in turn reacts with neutral ligands to give [OsH(CO)(CH₃N)(L)(PPh₃)₂]ClO₄ (L=CO, TIC, ETPO, PPh₃). Cationic [OsH(CO)₂(PPh₃)₃]+ and [OsH(TIC)₂(PPh₃)₃]+ can be prepared from the action of PPh₃ on [OsH(CO)₂(CH₃N)(PPh₃)₂]+ and TIC on OsH(O₂CCH₃)(PPh₃)₃ respectively. With base, [OsH(CO)(CH₃N)(PPh₃)₃]ClO4 affords OsH(OH)(CO)(PPh₃)₃ from which a series of hydroxide complexes OsH(OH)(CO)(L)(PPh₃)₂ (L=CO, TIC ETPO) can be obtained. The hydroxide group in OsH(OH)(CO)(PPh₃)₃ is cleaved by acids HX to yield OsHX(CO)(PPh₃)₃ (X=F, Br, Cl, I, CH₂, CF₂, SC₇H₇, OClO₃). Those members of the series with X=CN, N₃, OCN, SCN were obtained from OsH(OClO₃)(CO)(PPh₃)₃ and the appropriate anion. From the values of vCO for this series can be gained some understanding of the bonding properties of the anionic ligands."],"dc:format":["Scanned from print thesis"],"dc:identifier.uri":["https://hdl.handle.net/2292/2326"],"dc:language.iso":["en"],"dc:publisher":["ResearchSpace@Auckland"],"dc:relation.isreferencedby":["UoA217563"],"dc:rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"dc:rights.uri":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"dc:title":["Chemistry of low-valent osmium"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["PhD"],"thesis:institution_name":["The University of Auckland"]},"updated_at":"2026-07-24T01:06:10Z"}