title: Methylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄]: en route to mixed-thiolato bridged complexes

authors: Chong, Siew Huay

subjects: alkylation

abstract: Sequential and independent alkylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄] by RX followed by methylation with Me₂SO₄ led to the first successful isolation of novel diplatinum complexes [Pt₂(μ-SR) (μ -SCH₃) (PPh₃)₄](PF₆)₂ (3) (R= CH₂C₆H₅(a), CH₂CHCH₂ (b), C₅H₁₀CO₂CH₂CH₃(c), C₂H₄CO₂- CH₂CH₃(d), CH₂CH₂CN (e), C₂H₄CH-(O)₂C₂H₄ (f), and C₂H₄SC₆H₅(g)) with asymmetric thiolato bridges. The synthetic methodology can tolerate a range of electronically and sterically contrasting thiolate substituents with different chemical functionalities. The X-ray crystal structures of 3 a–c, g confirm the unusual heterodialkylation with two different thiolato bridging ligands in a syn–exo conformation. A secondary product [Pt₂(μ-SC₂H₄SC₆H₅) (μ-SCH₃)(PPh₃)₃](PF₆)₂ (4), which arises from intramolecular phosphine displacement by the thio pendant at the neighboring SC₂H₄SC₆H₅bridge, has been trapped and characterized. This is an unusual diplatinum complex with three different bridging thio ligands and three different phosphines.
The heteroalkylation is screened in situ by ESI-MS, and the resultant spectral data provide a convenient guide for one-pot syntheses of {M₂(SR) (SR’)} from {M₂S}. The isolation and X-ray crystal structure of a homoalkylated analogue [Pt₂(μ-SCH₃)₂(PPh₃)₄](PF₆)₂ (6) is included for comparison.

text: Methylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄]: en route to mixed-thiolato bridged complexes Sequential and independent alkylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄] by RX followed by methylation with Me₂SO₄ led to the first successful isolation of novel diplatinum complexes [Pt₂(μ-SR) (μ -SCH₃) (PPh₃)₄](PF₆)₂ (3) (R= CH₂C₆H₅(a), CH₂CHCH₂ (b), C₅H₁₀CO₂CH₂CH₃(c), C₂H₄CO₂- CH₂CH₃(d), CH₂CH₂CN (e), C₂H₄CH-(O)₂C₂H₄ (f), and C₂H₄SC₆H₅(g)) with asymmetric thiolato bridges. The synthetic methodology can tolerate a range of electronically and sterically contrasting thiolate substituents with different chemical functionalities. The X-ray crystal structures of 3 a–c, g confirm the unusual heterodialkylation with two different thiolato bridging ligands in a syn–exo conformation. A secondary product [Pt₂(μ-SC₂H₄SC₆H₅) (μ-SCH₃)(PPh₃)₃](PF₆)₂ (4), which arises from intramolecular phosphine displacement by the thio pendant at the neighboring SC₂H₄SC₆H₅bridge, has been trapped and characterized. This is an unusual diplatinum complex with three different bridging thio ligands and three different phosphines.
The heteroalkylation is screened in situ by ESI-MS, and the resultant spectral data provide a convenient guide for one-pot syntheses of {M₂(SR) (SR’)} from {M₂S}. The isolation and X-ray crystal structure of a homoalkylated analogue [Pt₂(μ-SCH₃)₂(PPh₃)₄](PF₆)₂ (6) is included for comparison.

year: 2006

title: A rhizomic approach to tourism destination evolution and transformation

authors: Pavlovich, Kathryn

subjects: networks

abstract: This paper critiques linear models of tourism destination evolution through exploring change as anti-hierarchical, self organising and locally inspired. Based upon the Deleuzian concept of networks as rhizomic, the longitudinal qualitative case study shows 100 years of evolution and transformation. The data demonstrated that through collaboration, network connections could be made in endless and unpredictable ways that then formed complex bundlings of network-based capabilities (multiplicities). These knowledge repositories emerged through the non-linear, heterogeneous and volume-filling connections inspired by the informal activities of everyday life. The data demonstrated that network transformation is a result of collaborative connection, and confirms Deleuze's imperative that all creative possibilities exist and new novelty is limited only by the absence of positive acts.

text: A rhizomic approach to tourism destination evolution and transformation This paper critiques linear models of tourism destination evolution through exploring change as anti-hierarchical, self organising and locally inspired. Based upon the Deleuzian concept of networks as rhizomic, the longitudinal qualitative case study shows 100 years of evolution and transformation. The data demonstrated that through collaboration, network connections could be made in endless and unpredictable ways that then formed complex bundlings of network-based capabilities (multiplicities). These knowledge repositories emerged through the non-linear, heterogeneous and volume-filling connections inspired by the informal activities of everyday life. The data demonstrated that network transformation is a result of collaborative connection, and confirms Deleuze's imperative that all creative possibilities exist and new novelty is limited only by the absence of positive acts.

year: 2014-04

title: Tauira Rangatahi Numeracy and Literacy Programme: Apps in Numeracy and Literacy Research

authors: Calder, Nigel Stuart

subjects: Youth Guarantee

abstract: A key aspect of tertiary education undertaken by Te Wananga o Aotearoa (TWoA) is re-establishing engagement and success in the rangatahi space through meeting the literacy and numeracy demands for programmes at levels 1–3. TWoA has Youth Guarantee programmes that deliver introductory Sport and Leisure and Contemporary Māori Arts programmes with embedded literacy and numeracy. The purpose of this research project was to investigate tauira rangatahi attitudes towards literacy and numeracy development through the application of appropriate cultural capital in conjunction with contemporary digital technologies. The research examined the influence of iPad apps on the beliefs and attitudes of Youth Guarantee tauira towards numeracy and literacy.

text: Tauira Rangatahi Numeracy and Literacy Programme: Apps in Numeracy and Literacy Research A key aspect of tertiary education undertaken by Te Wananga o Aotearoa (TWoA) is re-establishing engagement and success in the rangatahi space through meeting the literacy and numeracy demands for programmes at levels 1–3. TWoA has Youth Guarantee programmes that deliver introductory Sport and Leisure and Contemporary Māori Arts programmes with embedded literacy and numeracy. The purpose of this research project was to investigate tauira rangatahi attitudes towards literacy and numeracy development through the application of appropriate cultural capital in conjunction with contemporary digital technologies. The research examined the influence of iPad apps on the beliefs and attitudes of Youth Guarantee tauira towards numeracy and literacy.

year: 2014