title: Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

authors: Devoy, Sarah M.

subjects: platinum complexes

abstract: The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with a,x-dibromoalkanes Br(CH₂)nBr (n = 4, 5, 6, 8, 12) gave monoalkylated [Pt₂(μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂ (μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)12}]²⁺ was accessible from the reaction of [Pt₂ (μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)12Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at -18 degree C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂ (μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to x-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S} (PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)n_2CH=CH₂}(PPh₃)m]⁺ (m = 2 or 3; m – 4), most significant for n = 4, formed by elimination of HBr.

text: Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with a,x-dibromoalkanes Br(CH₂)nBr (n = 4, 5, 6, 8, 12) gave monoalkylated [Pt₂(μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂ (μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)12}]²⁺ was accessible from the reaction of [Pt₂ (μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)12Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at -18 degree C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂ (μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to x-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S} (PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)n_2CH=CH₂}(PPh₃)m]⁺ (m = 2 or 3; m – 4), most significant for n = 4, formed by elimination of HBr.

year: 2010

title: Sources of brand benefits in manufacturer-reseller B2B relationships

authors: Glynn, Mark

subjects: brands

abstract: Purpose – The aim of the paper is to develop a conceptual framework that explores the sources of manufacturer brand benefits for resellers. 
Design/methodology/approach – The paper reports a qualitative investigation where packaged goods resellers were interviewed about the benefits of manufacturer brands for their businesses. The qualitative data is analysed to develop several research propositions about the role of brands in reseller B2B relationships. 
Findings – A conceptual framework is developed that shows that manufacturers' brands provide financial, customer and managerial benefits for resellers. These benefits have an impact on reseller relationship outcomes with the manufacturer's brand, which include satisfaction, dependence, cooperation, commitment and trust. 
Practical implications – The conceptual framework provides a model that manufacturers of both major and minor brands can use to understand and manage these brand benefits in order to enhance the relationship outcomes with resellers. 
Originality/value – The paper responds to a need for empirical research to understand the role that brands play in channel relationships. It presents a conceptual framework that links manufacturer brand benefits to reseller relationship outcomes. The framework also includes major and minor brands as moderating variables and thus provides a basis for further quantitative research.

text: Sources of brand benefits in manufacturer-reseller B2B relationships Purpose – The aim of the paper is to develop a conceptual framework that explores the sources of manufacturer brand benefits for resellers. 
Design/methodology/approach – The paper reports a qualitative investigation where packaged goods resellers were interviewed about the benefits of manufacturer brands for their businesses. The qualitative data is analysed to develop several research propositions about the role of brands in reseller B2B relationships. 
Findings – A conceptual framework is developed that shows that manufacturers' brands provide financial, customer and managerial benefits for resellers. These benefits have an impact on reseller relationship outcomes with the manufacturer's brand, which include satisfaction, dependence, cooperation, commitment and trust. 
Practical implications – The conceptual framework provides a model that manufacturers of both major and minor brands can use to understand and manage these brand benefits in order to enhance the relationship outcomes with resellers. 
Originality/value – The paper responds to a need for empirical research to understand the role that brands play in channel relationships. It presents a conceptual framework that links manufacturer brand benefits to reseller relationship outcomes. The framework also includes major and minor brands as moderating variables and thus provides a basis for further quantitative research.

year: 2007

title: A report to iwi on the kaupapa Māori environmental outcomes and indicators kete

authors: Jefferies, Richard

subjects: New Zealand

abstract: Tangata whenua in Aotearoa have been largely excluded from participation in local government  planning since colonisation, but tikanga and Māori values have for the past two decades been acknowledged in resource management and local government legislation, especially the Resource Management Act, 1991 (RMA) and Local Government Act, 2002 (LGA). For example, the RMA has provisions in over 30 sections for councils to give effect to Māori interests.

In practice, however, there is widespread concern that despite these provisions, Māori are largely excluded from local government resource management processes and their values subordinated to those of the wider community, particularly western scientific values.

This report describes research that resulted in a kaupapa Māori outcomes and indicators framework, and associated methods, that can be used by iwi to assess the quality of statutory plans and the environmental performance of councils in their rohe.

text: A report to iwi on the kaupapa Māori environmental outcomes and indicators kete Tangata whenua in Aotearoa have been largely excluded from participation in local government  planning since colonisation, but tikanga and Māori values have for the past two decades been acknowledged in resource management and local government legislation, especially the Resource Management Act, 1991 (RMA) and Local Government Act, 2002 (LGA). For example, the RMA has provisions in over 30 sections for councils to give effect to Māori interests.

In practice, however, there is widespread concern that despite these provisions, Māori are largely excluded from local government resource management processes and their values subordinated to those of the wider community, particularly western scientific values.

This report describes research that resulted in a kaupapa Māori outcomes and indicators framework, and associated methods, that can be used by iwi to assess the quality of statutory plans and the environmental performance of councils in their rohe.

year: 2009-06-30