title: Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(II) and Zn(II) in an heterometallic {MPt₂S₂} core (M = Cd, Zn)

authors: Li, Zhaohui

subjects: chemistry

abstract: Two heterometallic complexes, [Pt₂MCl(bipy)(PPh₃)₄(μ₃-S)₂][PF₆] (M = Zn, 2, Cd, 3) were synthesized from [Pt₂(PPh₃)₄(μ-S)₂] and characterized by single-crystal X-ray diffraction and electrospray ionization mass spectrometry. Two unusual square-based pyramidal (sbp) Zn(II) and Cd(II) structures are evident. VT 31P-{1H} NMR studies showed that 2 and 3 are fluxional at rt whereby rapid ligand exchange takes place by a non-dissociative mechanism. At intermediate temperatures, this motion slows down to a flipping movement of the {Pt₂S₂} ligand. At 183 K, all four phosphines are inequivalent in a distorted sbp model similar to that observed in the solid state. Nonlocal density functional theory calculations reveal that the formation of a trigonal bipyramidal intermediate in the fluxional process is favored over that of the tetrahedral species for both 2 and 3. The M–Cl (M = Zn, Cd) bonds are notably strong.

text: Ligand-stabilization of an unusual square-based pyramidal geometry of Cd(II) and Zn(II) in an heterometallic {MPt₂S₂} core (M = Cd, Zn) Two heterometallic complexes, [Pt₂MCl(bipy)(PPh₃)₄(μ₃-S)₂][PF₆] (M = Zn, 2, Cd, 3) were synthesized from [Pt₂(PPh₃)₄(μ-S)₂] and characterized by single-crystal X-ray diffraction and electrospray ionization mass spectrometry. Two unusual square-based pyramidal (sbp) Zn(II) and Cd(II) structures are evident. VT 31P-{1H} NMR studies showed that 2 and 3 are fluxional at rt whereby rapid ligand exchange takes place by a non-dissociative mechanism. At intermediate temperatures, this motion slows down to a flipping movement of the {Pt₂S₂} ligand. At 183 K, all four phosphines are inequivalent in a distorted sbp model similar to that observed in the solid state. Nonlocal density functional theory calculations reveal that the formation of a trigonal bipyramidal intermediate in the fluxional process is favored over that of the tetrahedral species for both 2 and 3. The M–Cl (M = Zn, Cd) bonds are notably strong.

year: 2000

title: Surfing life: surface, substructure and the commodification of the sublime

authors: lisahunter

subjects: book review

abstract: Mark Stranger’s first words of his book Surfing Life dedicate the work to his father saying ‘He started this whole thing with the sea for me’. Flicking through the book to get the flavour of ‘this thing with the sea’, I was struck by the appendices*one listing Australian surfing places I know*such as Torquay in Victoria and Lennox Heads in New South Wales and another listing people involved in his extensive empirical material that included a year of ‘travelling around Australia living in a tent’ (xi), while he conducted fieldwork. Some of the names I know and in others I recognize the characters I’ve met. There are significant names from the public surfing world, like Pam Burridge and Gail Austen, which are famous in the competitive world. There are also pseudonymed characters such as Blue, a ‘female less than 26, desert location, long-term resident of the desert camp, bodyboarder’ (257). I recognized such characters in my own research and my own experience of surfing and could relate to some of his ‘insider’ perspectives. These locations, interview material and his own experiences act as the water for his sea washing through his book. This water mixes with contemporary social theory to finish in an argument that subcultures, such as surfing, are ‘integral to the broader dialectical processes of postmodernization’ (253) or if you like ‘an early agent of postmodernization’ (254).

text: Surfing life: surface, substructure and the commodification of the sublime Mark Stranger’s first words of his book Surfing Life dedicate the work to his father saying ‘He started this whole thing with the sea for me’. Flicking through the book to get the flavour of ‘this thing with the sea’, I was struck by the appendices*one listing Australian surfing places I know*such as Torquay in Victoria and Lennox Heads in New South Wales and another listing people involved in his extensive empirical material that included a year of ‘travelling around Australia living in a tent’ (xi), while he conducted fieldwork. Some of the names I know and in others I recognize the characters I’ve met. There are significant names from the public surfing world, like Pam Burridge and Gail Austen, which are famous in the competitive world. There are also pseudonymed characters such as Blue, a ‘female less than 26, desert location, long-term resident of the desert camp, bodyboarder’ (257). I recognized such characters in my own research and my own experience of surfing and could relate to some of his ‘insider’ perspectives. These locations, interview material and his own experiences act as the water for his sea washing through his book. This water mixes with contemporary social theory to finish in an argument that subcultures, such as surfing, are ‘integral to the broader dialectical processes of postmodernization’ (253) or if you like ‘an early agent of postmodernization’ (254).

year: 2012

title: Formulaic Discourse Patterning in Mōteatea

authors: Roa, Te Raukura o Te Rangimarie

subjects: mōteatea

abstract: Oral formulaic composition, which involves the use of communally owned formulae of various kinds, is a common feature of verbal arts produced in many different languages. It is particularly associated with pre-literate cultures and tends to be gradually replaced by more individualistic verbal art forms when societies become literate. There are very few publications in which the analysis of mōteatea (Māori laments) is linked explicitly to oral formulaic theory. Nevertheless, there is, I believe, sufficient evidence in published sources to indicate that traditional mōteatea (defined here as mōteatea that are not fundamentally influenced by European cultural beliefs and practices) exhibit evidence of regularly recurring, conventional themes (such as death, separation, loss and travel) and motifs (such as the setting sun, the presence of rain or mist and sleeplessness).  There is, however, considerably less evidence that traditional mōteatea make extensive use of verbal formulae, that is, of the same or very similar groups of words derived from a common store of poetic resources. Although there are references in the literature to the conventionalized use of language in mōteatea, and although it has been claimed that there are at least some commonly recurring verbal expressions, this is by no means evidence of reliance on a common stock of verbal formulae. Indeed, no attempt has hitherto been made to define precisely what might be meant by the term 'oral formula' in the context of compositions in te reo Māori, something that is clearly required in view, in particular, of the fact that the phrasal structure of the language means that certain groupings (e.g. i te X; ki te X) are very likely to occur in certain contexts irrespective of genre. Furthermore, in the literature on oral formulaic composition, oral formulae are generally linked to particular metrical conditions and there is, it is argued here, no convincing empirically-based evidence that mōteatea conform to any common metrical structure or structures (see Chapters 2 and 4).

In the context of a critical review of selected literature on oral formulaic theory (Chapter 2) and mōteatea (Chapter 3), this thesis sets out to test the hypothesis that traditional mōteatea were composed, in whole or in large part, from a common stock of oral formulae. The conclusion, based on analysis of a selection of mōteatea included in Ngā mōteatea, a collection initially established by Sir Apirana Ngata, is that this hypothesis must be rejected (Chapter 4). However, a model derived from a review of selected literature on discourse structure (Chapter 5) was also applied to the analysis of a sample of these mōteatea (Chapter 6). On the basis of this analysis, it is concluded that they exhibit one of two very similar discourse prototypes, each of which involves a particular combination of discourse elements. What distinguishes the two prototypes is the fact that only one of them is characterized by the inclusion of hortatory sections in which the poet urges one or more of the protagonists to undergo one or more steps or stages required to achieve a particular outcome, such as entry into the spirit world or vengeance for death and/ or humiliation.

text: Formulaic Discourse Patterning in Mōteatea Oral formulaic composition, which involves the use of communally owned formulae of various kinds, is a common feature of verbal arts produced in many different languages. It is particularly associated with pre-literate cultures and tends to be gradually replaced by more individualistic verbal art forms when societies become literate. There are very few publications in which the analysis of mōteatea (Māori laments) is linked explicitly to oral formulaic theory. Nevertheless, there is, I believe, sufficient evidence in published sources to indicate that traditional mōteatea (defined here as mōteatea that are not fundamentally influenced by European cultural beliefs and practices) exhibit evidence of regularly recurring, conventional themes (such as death, separation, loss and travel) and motifs (such as the setting sun, the presence of rain or mist and sleeplessness).  There is, however, considerably less evidence that traditional mōteatea make extensive use of verbal formulae, that is, of the same or very similar groups of words derived from a common store of poetic resources. Although there are references in the literature to the conventionalized use of language in mōteatea, and although it has been claimed that there are at least some commonly recurring verbal expressions, this is by no means evidence of reliance on a common stock of verbal formulae. Indeed, no attempt has hitherto been made to define precisely what might be meant by the term 'oral formula' in the context of compositions in te reo Māori, something that is clearly required in view, in particular, of the fact that the phrasal structure of the language means that certain groupings (e.g. i te X; ki te X) are very likely to occur in certain contexts irrespective of genre. Furthermore, in the literature on oral formulaic composition, oral formulae are generally linked to particular metrical conditions and there is, it is argued here, no convincing empirically-based evidence that mōteatea conform to any common metrical structure or structures (see Chapters 2 and 4).

In the context of a critical review of selected literature on oral formulaic theory (Chapter 2) and mōteatea (Chapter 3), this thesis sets out to test the hypothesis that traditional mōteatea were composed, in whole or in large part, from a common stock of oral formulae. The conclusion, based on analysis of a selection of mōteatea included in Ngā mōteatea, a collection initially established by Sir Apirana Ngata, is that this hypothesis must be rejected (Chapter 4). However, a model derived from a review of selected literature on discourse structure (Chapter 5) was also applied to the analysis of a sample of these mōteatea (Chapter 6). On the basis of this analysis, it is concluded that they exhibit one of two very similar discourse prototypes, each of which involves a particular combination of discourse elements. What distinguishes the two prototypes is the fact that only one of them is characterized by the inclusion of hortatory sections in which the poet urges one or more of the protagonists to undergo one or more steps or stages required to achieve a particular outcome, such as entry into the spirit world or vengeance for death and/ or humiliation.

year: 2008