title: Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II)

authors: Dowling-Mitchell, Sacha A.M.

abstract: Reactions of the platinum complexes cis-[PtCl₂(PPh₃)₂ ], [PtCl₂(dppf)], or [PtCl₂(dppe)], and the palladium complexes, [PdCl₂(PPh₃)₂] or [PdCl₂(dppe)], with bis(cyanomethyl)sulfone NCCH₂SO₂ CH₂CN  in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3- dioxide complexes [M{CH(CN)SO₂ CH(CN)}L₂ ] (M = Pd, Pt) in good yields and purities. ¹H and ³¹P{¹H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO₂CH(CN)}(PPh₃)₂] showed it to be of the cis isomer, the ﬁrst structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3-dioxide complexes that have puckered rings. Factors inﬂuencing the relative abundances of the two isomers of [Pd{CH(CN)SO₂CH(CN)}(PR₃)₂] have been investigated by means of NMR spectroscopy and DFT calculations.

text: Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II) Reactions of the platinum complexes cis-[PtCl₂(PPh₃)₂ ], [PtCl₂(dppf)], or [PtCl₂(dppe)], and the palladium complexes, [PdCl₂(PPh₃)₂] or [PdCl₂(dppe)], with bis(cyanomethyl)sulfone NCCH₂SO₂ CH₂CN  in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3- dioxide complexes [M{CH(CN)SO₂ CH(CN)}L₂ ] (M = Pd, Pt) in good yields and purities. ¹H and ³¹P{¹H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO₂CH(CN)}(PPh₃)₂] showed it to be of the cis isomer, the ﬁrst structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3-dioxide complexes that have puckered rings. Factors inﬂuencing the relative abundances of the two isomers of [Pd{CH(CN)SO₂CH(CN)}(PR₃)₂] have been investigated by means of NMR spectroscopy and DFT calculations.

year: 2012

title: The development of multiplicative thinking and proportional reasoning: Models of conceptual learning and transfer

authors: Wright, Vincent John

subjects: proportional reasoning

abstract: This thesis considers the development of multiplicative thinking and proportional reasoning from two perspectives. Firstly, it examines the research literature on progressions in conceptual understanding to create a Hypothetical Learning Trajectory (HLT). Secondly, it surveys modern views of how transfer by learners occurs in and between situations, contrasting object views of abstraction with knowledge in pieces views.
Case studies of six students aged 11-13 years illustrate conceptual changes that occur during the course of a school year. The students are involved in a design experiment in which I (the researcher) co-teach with the classroom teacher. The students represent a mix of gender, ethnicity and level of achievement. Comparison of the HLT with the actual learning trajectory for each student establishes its validity as a generic growth path.
Examination of the data suggests that two models of learning and by inference, transfer, describe the conceptual development of the students. There is consideration of students’ use of anticipated actions on physical and imaged embodiments as objects of thought with a focus on the significance of object creation for conceptual growth, and the encapsulation, completeness and contextual detachment of objects. 
There is broad consistency in students’ progress through the phases of the HTL within each sub-construct though the developmental patterns of individual are variable and temporal alignment across the sub-constructs does not uniformly hold. Some consistency of order effect in concept development is noted. Discussion on the limitations of the HTL includes the difference between knowledge types from a pedagogical perspective, absence of significant model-representation-situation transfer, and order relations in conceptual development.
Considerable situational variation occurs as students solve problems that involve applications of the same concepts. Partial construction of concepts is common. This was true of all learners, irrespective of level of achievement. High-achieving students more readily anticipate actions and trust these anticipations as objects of thought than middle and low achievers. The data supports knowledge in pieces views of conceptual development. Complexity for learners in observing affordances in situations, and in co-ordinating the fine-grained knowledge required, explains the difficulty of transfer. While supporting the anticipation of action as significant from a learning perspective the research suggests that expertise in applying concepts involves a process of noticing similarity across contextually bound situations and cueing appropriate knowledge resources.

text: The development of multiplicative thinking and proportional reasoning: Models of conceptual learning and transfer This thesis considers the development of multiplicative thinking and proportional reasoning from two perspectives. Firstly, it examines the research literature on progressions in conceptual understanding to create a Hypothetical Learning Trajectory (HLT). Secondly, it surveys modern views of how transfer by learners occurs in and between situations, contrasting object views of abstraction with knowledge in pieces views.
Case studies of six students aged 11-13 years illustrate conceptual changes that occur during the course of a school year. The students are involved in a design experiment in which I (the researcher) co-teach with the classroom teacher. The students represent a mix of gender, ethnicity and level of achievement. Comparison of the HLT with the actual learning trajectory for each student establishes its validity as a generic growth path.
Examination of the data suggests that two models of learning and by inference, transfer, describe the conceptual development of the students. There is consideration of students’ use of anticipated actions on physical and imaged embodiments as objects of thought with a focus on the significance of object creation for conceptual growth, and the encapsulation, completeness and contextual detachment of objects. 
There is broad consistency in students’ progress through the phases of the HTL within each sub-construct though the developmental patterns of individual are variable and temporal alignment across the sub-constructs does not uniformly hold. Some consistency of order effect in concept development is noted. Discussion on the limitations of the HTL includes the difference between knowledge types from a pedagogical perspective, absence of significant model-representation-situation transfer, and order relations in conceptual development.
Considerable situational variation occurs as students solve problems that involve applications of the same concepts. Partial construction of concepts is common. This was true of all learners, irrespective of level of achievement. High-achieving students more readily anticipate actions and trust these anticipations as objects of thought than middle and low achievers. The data supports knowledge in pieces views of conceptual development. Complexity for learners in observing affordances in situations, and in co-ordinating the fine-grained knowledge required, explains the difficulty of transfer. While supporting the anticipation of action as significant from a learning perspective the research suggests that expertise in applying concepts involves a process of noticing similarity across contextually bound situations and cueing appropriate knowledge resources.

year: 2011

title: Civilisation, settlers and wanderers: Law, politics and mobility in nineteenth century New Zealand and Australia

authors: Seuffert, Nan

subjects: colonization

abstract: Mobility was constitutive of the 19th century British colonial period in the Pacific. The circulation of capital and commodities, technologies of transportation and communication, travelling ideologies and systems of governance and surveillance, as well as the movement of explorers, whalers, labourers, settlers, missionaries, colonial administrators, convicts, soldiers, sojourners, immigrants, and transnational and displaced indigenous peoples, all shaped the politics and the period (see Ballantyne 2009: 7-8; Seuffert 2006: 7-8; Arrighi 1994: 48-58). Highly mobile British and European immigrants with money or skills were termed 'settlers', with associated connotations of stabilising and civilising influences. Missionaries and colonial officials who were integral to colonisation were also often highly mobile, carrying policies and regulatory regimes with them, and their colonial roles as 'civilising' influences included 'settling' and advancing the position of indigenous and other colonised peoples. In contrast, the mobility of poor whites and racialised populations - such as 'Melanesian' indentured labourers (Banivanua-Mar 2007: 3-4)2, Indian workers, displaced indigenous peoples and 'sojourner' Chinese - attracted the attention of law (and policy) makers and institutional authorities and were subjected to various forms of surveillance, regulation and policing designed to constrain and contain them.

text: Civilisation, settlers and wanderers: Law, politics and mobility in nineteenth century New Zealand and Australia Mobility was constitutive of the 19th century British colonial period in the Pacific. The circulation of capital and commodities, technologies of transportation and communication, travelling ideologies and systems of governance and surveillance, as well as the movement of explorers, whalers, labourers, settlers, missionaries, colonial administrators, convicts, soldiers, sojourners, immigrants, and transnational and displaced indigenous peoples, all shaped the politics and the period (see Ballantyne 2009: 7-8; Seuffert 2006: 7-8; Arrighi 1994: 48-58). Highly mobile British and European immigrants with money or skills were termed 'settlers', with associated connotations of stabilising and civilising influences. Missionaries and colonial officials who were integral to colonisation were also often highly mobile, carrying policies and regulatory regimes with them, and their colonial roles as 'civilising' influences included 'settling' and advancing the position of indigenous and other colonised peoples. In contrast, the mobility of poor whites and racialised populations - such as 'Melanesian' indentured labourers (Banivanua-Mar 2007: 3-4)2, Indian workers, displaced indigenous peoples and 'sojourner' Chinese - attracted the attention of law (and policy) makers and institutional authorities and were subjected to various forms of surveillance, regulation and policing designed to constrain and contain them.

year: 2011