title: Some metallacyclic complexes of the late transition metals

authors: Oliver, Allen G.

abstract: The principal aim of this thesis is the synthesis and characterisation of four-membered metallacyclic complexes. Reactions of square-planar palladium(II), platinum(II) and gold(III) dihalide complexes with a variety of amides, some in the presence of silver(I) oxide are discussed.

Chapter one reviews the literature of small-ring metallacyclic chemistry, in particular the synthesis of four-membered metallacycles, as they are, in the main, the complexes that are further reported throughout the remainder of the thesis.

Chapter two reports the synthesis of four-membered metallalactam complexes [M{N(Ph)C(O)CHC(O)Ph}L₂] (2.11 - 2.15) formed from the reactions of square-planar L₂MCl₂ complexes [M = Pt, Pd, L = PPh₃, L₂ = 1,5-cyclooctadiene (COD), 1,2-bis(diphenylphosphino)ethane (dppe), 2,2’-bipyridine (bipy)] with 2-benzoylacetanilide [PhC(O)CH₂C(O)NHPh] in the presence of silver(I) oxide. The X-ray crystal structure of [Pd{N(Ph)C(O)CHC(O)Ph}(bipy)].CH₂Cl₂ (2.14.CH₂Cl₂) was determined to confirm the geometry of the compounds. The reactions of acetoacetamide [NH₂C(O)CH₂C(O)CH₃] with cis-[PtCl₂ (PPh₃)₂], [PtCl₂(dppe)] and [PdCl₂(bipy)] (2.16 - 2.18) in the presence of silver(I) oxide are also discussed.

Chapter three describes the isolation and characterisation of a platinum(II)-amidate complex, believed to be the first characterised intermediate in silver(I) oxide mediated reactions. For short reaction times the complex cis-[Pt{N(C(O)CH₂CN)(CO₂Et)}Cl(PPh₃)₂] (3.4) can be isolated from the reaction mixture of cis-[PtCl₂(PPh₃)₂] with N-cyanoacetylurethane [NCCH₂C(O)NHCO₂Et] in the presence of silver(I) oxide. For long reaction times this synthesis is known to afford the four-membered metallalactam [Pt{N(CO₂Et)C(O)CHCN}(PPh₃)₂].

Chapter four details the synthesis and characterisation of four-membered gold(III) lactam complexes. A series of metallalactam complexes were characterised from the reaction of [LAuCl₂] [L = {C₆H₃(CH₂NMe₂)-2-OMe-5} or {C₆H₄(CH₂NMe₂)-2}] with N-cyanoacetylurethane, 2-benzoylacetanilide, acetoacetanilide or acetoacetamide in the presence of silver(I) oxide. A representative of these gold(III) metallacycles, [{C₆H₄-CH₂NMe₂-2}Au{N(Ph)C(O)CHC(O)CH₃}] (4.13), was structurally characterised. A novel and unprecedented dimerisation occurred with [{C₆H₃-CH₂NMe₂-2-OMe5}Au{N(CO₂Et)C(O)CHCN}], that formed an eight-membered metallacycle (4.15) which was characterised by an X-ray diffraction study.

The reactions of cis-[PtCl₂(PPh₃)₂] with either cyanoacetic acid or phenoxyacetic acid in the presence of silver(I) oxide are reported in chapter five. The reaction of phenoxyacetic acid with cis-[PtCl₂(PPh₃)₂] was found to form the simple platinum(II) bis(carboxylate) complex, cis-[Pt(O₂CCH₂OPh)₂(PPh₃)₂] (5.9). Conversely, cyanoacetic acid undergoes a novel decarboxylation reaction which results in the formation of the platinum(II) bis(alkyl) complex cis-[Pt(CH₂CN)₂PPh₃)₂] (5.7). The X-ray crystal structures of these two complexes are described.

Chapter six discusses the triethylamine-mediated syntheses of four-membered metallalactam complexes. The reactions of cyanoacetylurea [NH₂C(O)NHC(O)CH₂CN] with cis-[PtCl₂(PPh₃)₂], [PtCl₂(COD)], [PtCl₂(dppe)] and [PdCl₂(dppe)] in the presence of triethylamine and details of their characterisation are described. One complex, cis-[Pt{N(C(O)NH₂)C(O)CHCN}(PPh₃)₂] (6.5), was structurally characterised and was found to crystallise as an H-bonded dimer. The reactions of N-cyanoacetylurethane, 2-benzoylacetanilide and acetoacetanilide with cis-[PtCl₂(PPh₃)₂] in the presence of silver(I) oxide are known to give well-characterised four-membered metallalactam complexes. The results of the reactions of these compounds when reacted under similar conditions, but with triethylamine as the base and halide abstractor, are also discussed.

Chapter seven describes a selection of four crystal structures. The X-ray structure of the first coordinatively saturated iridaureylene complex, [Ir{N(Me)C(O)NAc}(Cp*)(PPh₃)] (7.4), which is isoelectronic with four-membered metallalactam complexes, is described. The complex was found to adopt a “bar-stool” geometry. The structures of the complexes, [Rh{O₂CC₆H₄-S-2}Cp*]₂ (7.8) and [Ru{O₂CC₆H₄-S-2}(p-cymene)]₂ (7.9) were studied and found to be dimeric compounds. The complexes were found to adopt a pseudo-octahedral geometry, with a three-coordinate, bridging thiolate sulfur. The fourth structural analysis was that of the novel chelation product of cis-[Pt{NCH₂CH₂C(O)}₂(PPh₃)₂] with uranyl nitrate [UO₂(NO₃)₂]. The complex was found to form an eight-membered heterocycle (7.15), with the platinum bis(lactam) complex coordinating to the uranium via the lactam oxygen atoms.

text: Some metallacyclic complexes of the late transition metals The principal aim of this thesis is the synthesis and characterisation of four-membered metallacyclic complexes. Reactions of square-planar palladium(II), platinum(II) and gold(III) dihalide complexes with a variety of amides, some in the presence of silver(I) oxide are discussed.

Chapter one reviews the literature of small-ring metallacyclic chemistry, in particular the synthesis of four-membered metallacycles, as they are, in the main, the complexes that are further reported throughout the remainder of the thesis.

Chapter two reports the synthesis of four-membered metallalactam complexes [M{N(Ph)C(O)CHC(O)Ph}L₂] (2.11 - 2.15) formed from the reactions of square-planar L₂MCl₂ complexes [M = Pt, Pd, L = PPh₃, L₂ = 1,5-cyclooctadiene (COD), 1,2-bis(diphenylphosphino)ethane (dppe), 2,2’-bipyridine (bipy)] with 2-benzoylacetanilide [PhC(O)CH₂C(O)NHPh] in the presence of silver(I) oxide. The X-ray crystal structure of [Pd{N(Ph)C(O)CHC(O)Ph}(bipy)].CH₂Cl₂ (2.14.CH₂Cl₂) was determined to confirm the geometry of the compounds. The reactions of acetoacetamide [NH₂C(O)CH₂C(O)CH₃] with cis-[PtCl₂ (PPh₃)₂], [PtCl₂(dppe)] and [PdCl₂(bipy)] (2.16 - 2.18) in the presence of silver(I) oxide are also discussed.

Chapter three describes the isolation and characterisation of a platinum(II)-amidate complex, believed to be the first characterised intermediate in silver(I) oxide mediated reactions. For short reaction times the complex cis-[Pt{N(C(O)CH₂CN)(CO₂Et)}Cl(PPh₃)₂] (3.4) can be isolated from the reaction mixture of cis-[PtCl₂(PPh₃)₂] with N-cyanoacetylurethane [NCCH₂C(O)NHCO₂Et] in the presence of silver(I) oxide. For long reaction times this synthesis is known to afford the four-membered metallalactam [Pt{N(CO₂Et)C(O)CHCN}(PPh₃)₂].

Chapter four details the synthesis and characterisation of four-membered gold(III) lactam complexes. A series of metallalactam complexes were characterised from the reaction of [LAuCl₂] [L = {C₆H₃(CH₂NMe₂)-2-OMe-5} or {C₆H₄(CH₂NMe₂)-2}] with N-cyanoacetylurethane, 2-benzoylacetanilide, acetoacetanilide or acetoacetamide in the presence of silver(I) oxide. A representative of these gold(III) metallacycles, [{C₆H₄-CH₂NMe₂-2}Au{N(Ph)C(O)CHC(O)CH₃}] (4.13), was structurally characterised. A novel and unprecedented dimerisation occurred with [{C₆H₃-CH₂NMe₂-2-OMe5}Au{N(CO₂Et)C(O)CHCN}], that formed an eight-membered metallacycle (4.15) which was characterised by an X-ray diffraction study.

The reactions of cis-[PtCl₂(PPh₃)₂] with either cyanoacetic acid or phenoxyacetic acid in the presence of silver(I) oxide are reported in chapter five. The reaction of phenoxyacetic acid with cis-[PtCl₂(PPh₃)₂] was found to form the simple platinum(II) bis(carboxylate) complex, cis-[Pt(O₂CCH₂OPh)₂(PPh₃)₂] (5.9). Conversely, cyanoacetic acid undergoes a novel decarboxylation reaction which results in the formation of the platinum(II) bis(alkyl) complex cis-[Pt(CH₂CN)₂PPh₃)₂] (5.7). The X-ray crystal structures of these two complexes are described.

Chapter six discusses the triethylamine-mediated syntheses of four-membered metallalactam complexes. The reactions of cyanoacetylurea [NH₂C(O)NHC(O)CH₂CN] with cis-[PtCl₂(PPh₃)₂], [PtCl₂(COD)], [PtCl₂(dppe)] and [PdCl₂(dppe)] in the presence of triethylamine and details of their characterisation are described. One complex, cis-[Pt{N(C(O)NH₂)C(O)CHCN}(PPh₃)₂] (6.5), was structurally characterised and was found to crystallise as an H-bonded dimer. The reactions of N-cyanoacetylurethane, 2-benzoylacetanilide and acetoacetanilide with cis-[PtCl₂(PPh₃)₂] in the presence of silver(I) oxide are known to give well-characterised four-membered metallalactam complexes. The results of the reactions of these compounds when reacted under similar conditions, but with triethylamine as the base and halide abstractor, are also discussed.

Chapter seven describes a selection of four crystal structures. The X-ray structure of the first coordinatively saturated iridaureylene complex, [Ir{N(Me)C(O)NAc}(Cp*)(PPh₃)] (7.4), which is isoelectronic with four-membered metallalactam complexes, is described. The complex was found to adopt a “bar-stool” geometry. The structures of the complexes, [Rh{O₂CC₆H₄-S-2}Cp*]₂ (7.8) and [Ru{O₂CC₆H₄-S-2}(p-cymene)]₂ (7.9) were studied and found to be dimeric compounds. The complexes were found to adopt a pseudo-octahedral geometry, with a three-coordinate, bridging thiolate sulfur. The fourth structural analysis was that of the novel chelation product of cis-[Pt{NCH₂CH₂C(O)}₂(PPh₃)₂] with uranyl nitrate [UO₂(NO₃)₂]. The complex was found to form an eight-membered heterocycle (7.15), with the platinum bis(lactam) complex coordinating to the uranium via the lactam oxygen atoms.

year: 1999

title: How to survive a plague of flesh-eating rats: An introductory guide to studying remediated ‎gameplay imaginations of medieval folklore and beliefs in A Plague Tale: Innocence

authors: Schott, Gareth R.

abstract: Popular digital games such as Assassin’s Creed: Origins (2017), Total War: Three Kingdoms (2019), and Red: Dead Redemption (2010) possess merit for their faithful and authentic interactive representations of elements of the past that furnish games with pedagogical value. Both digital game studies and historical game studies have contributed research furthering understanding of the pedagogical value and applications of historical games for students’ learning of history in school education, particularly secondary schools and universities (Kee, 2014, McCall, 2013, &amp; Schrier, 2014). Despite the growing interest in the new forms of knowledge contained within games, and gameplay, the educational application of historical digital games can be limited to supplementary visual aids that do not fully account for the range and forms of historical investigation associated with the game development process. We forward a multi-modal perspective on the varied ways in which historical knowledge is present in both game design and the gameplay experience. Our approach is demonstrated with one of several under-investigated (yet valuable) modes of historical exploration, namely ‘Imaginative History.’ This is achieved using images from several sequences of recorded game footage in the Medieval historical fantasy game A Plague Tale: Innocence as a case example alongside supporting historical literature. This Medieval game is suitable for addressing this conference’s theme of crises or disasters as it is set in a re-imagination of the Black Death plague roughly within the south-western region of fourteenth century France, but one that personifies the real Black Death with a plague of supernatural flesh-eating rats and places players into the role of two fictional orphan children. This presentation seeks to demonstrate historical games’ value for teaching and learning by discussing A Plague Tale: Innocence’s fantastical adaptation of the plague as a model for exploring the role of re-mediation, and subversion, of past pre-modern folklore imaginations and beliefs. Fantasy or folkloric treatment of historical events or periods can provide insight into the experiential dimensions of a period in history re-told as an interactive folktale.

text: How to survive a plague of flesh-eating rats: An introductory guide to studying remediated ‎gameplay imaginations of medieval folklore and beliefs in A Plague Tale: Innocence Popular digital games such as Assassin’s Creed: Origins (2017), Total War: Three Kingdoms (2019), and Red: Dead Redemption (2010) possess merit for their faithful and authentic interactive representations of elements of the past that furnish games with pedagogical value. Both digital game studies and historical game studies have contributed research furthering understanding of the pedagogical value and applications of historical games for students’ learning of history in school education, particularly secondary schools and universities (Kee, 2014, McCall, 2013, &amp; Schrier, 2014). Despite the growing interest in the new forms of knowledge contained within games, and gameplay, the educational application of historical digital games can be limited to supplementary visual aids that do not fully account for the range and forms of historical investigation associated with the game development process. We forward a multi-modal perspective on the varied ways in which historical knowledge is present in both game design and the gameplay experience. Our approach is demonstrated with one of several under-investigated (yet valuable) modes of historical exploration, namely ‘Imaginative History.’ This is achieved using images from several sequences of recorded game footage in the Medieval historical fantasy game A Plague Tale: Innocence as a case example alongside supporting historical literature. This Medieval game is suitable for addressing this conference’s theme of crises or disasters as it is set in a re-imagination of the Black Death plague roughly within the south-western region of fourteenth century France, but one that personifies the real Black Death with a plague of supernatural flesh-eating rats and places players into the role of two fictional orphan children. This presentation seeks to demonstrate historical games’ value for teaching and learning by discussing A Plague Tale: Innocence’s fantastical adaptation of the plague as a model for exploring the role of re-mediation, and subversion, of past pre-modern folklore imaginations and beliefs. Fantasy or folkloric treatment of historical events or periods can provide insight into the experiential dimensions of a period in history re-told as an interactive folktale.

year: 2021

title: The peopling and development of Aotearoa New Zealand: A demographic history, 1769-2020

authors: Pool, Ian

subjects: Aotearoa

abstract: This unpublished manuscript is the first demographic history of Aotearoa New Zealand, integrating 250 years of Māori and non-Māori data. It explores how development, in the broadest social, cultural and economic sense drove population changes, but was in turn driven by demographic factors. Based on extensively referenced research and analysis, the timeline starts with the earliest European settlement and finishes with the multicultural and aging society of the first decades of the twenty-first century.  It encompasses momentous changes, including: successive waves of migration, European settler demographic dominance occurring rapidly through natural increase, Māori nineteenth century cultural devastation and population decline, and twentieth-century resurgence, the Māori rural/urban exodus beginning in the 1940s, and the post-war non-Māori baby boom and baby bust. At each stage, this book demonstrates how profoundly the story of Aotearoa New Zealand is also the demographic story of its peopling.

text: The peopling and development of Aotearoa New Zealand: A demographic history, 1769-2020 This unpublished manuscript is the first demographic history of Aotearoa New Zealand, integrating 250 years of Māori and non-Māori data. It explores how development, in the broadest social, cultural and economic sense drove population changes, but was in turn driven by demographic factors. Based on extensively referenced research and analysis, the timeline starts with the earliest European settlement and finishes with the multicultural and aging society of the first decades of the twenty-first century.  It encompasses momentous changes, including: successive waves of migration, European settler demographic dominance occurring rapidly through natural increase, Māori nineteenth century cultural devastation and population decline, and twentieth-century resurgence, the Māori rural/urban exodus beginning in the 1940s, and the post-war non-Māori baby boom and baby bust. At each stage, this book demonstrates how profoundly the story of Aotearoa New Zealand is also the demographic story of its peopling.

year: 2026