title: Synthesis of Piano Stool Complexes Employing the Pentafluorophenyl-Substituted Diphosphine (C₆F₅)₂PCH₂P(C₆F₅)₂ and the Effect of Phosphine Modifiers on Hydrogen Transfer Catalysis

authors: Marr, Andrew C.

subjects: chemistry

abstract: Ruthenium, rhodium, and iridium piano stool complexes of the pentafluorophenyl-substituted diphosphine (C₆F₅)₂PCH₂P(C₆F₅)₂ (2) have been prepared and structurally characterized by single-crystal X-ray diffraction. The η⁵,κP-Cp−P tethered complex [{(η5,κP-C₅Me₄CH₂C₆F₄-2-P(C₆F₅)CH₂P(C₆F₅)₂}RhCl₂] (9), in which only one phosphorus is coordinated to the rhodium, was prepared by thermolysis of a slurry of [Cp*RhCl(μ-Cl)]₂ and 2 and was structurally characterized by single-crystal X-ray diffraction. The tethering occurs by intramolecular dehydrofluorinative coupling of the η⁵-pentamethylcyclopentadienyl ligand and κP,κP-coordinated 2. The geometric changes that occur on tethering force dissociation of one of the phosphorus atoms. The effects of introducing phosphine ligands to the coordination sphere of piano stool hydrogen transfer catalysts have been studied. The complexes of fluorinated phosphine complexes are found to transfer hydrogen at rates that compare favorably with leading catalysts, particularly when the phosphine and cyclopentadienyl functionalities are tethered. The highly chelating η⁵,κP,κL-Cp−PP complex [(η⁵,κP,κP-C₅Me₄CH₂-2-C₅F₃N-4-PPhCH₂CH₂PPh₂)RhCl]BF₄ (1) was found to outperform all other complexes tested. The mechanism of hydrogen transfer catalyzed by piano stool phosphine complexes is discussed with reference to the trends in activity observed.

text: Synthesis of Piano Stool Complexes Employing the Pentafluorophenyl-Substituted Diphosphine (C₆F₅)₂PCH₂P(C₆F₅)₂ and the Effect of Phosphine Modifiers on Hydrogen Transfer Catalysis Ruthenium, rhodium, and iridium piano stool complexes of the pentafluorophenyl-substituted diphosphine (C₆F₅)₂PCH₂P(C₆F₅)₂ (2) have been prepared and structurally characterized by single-crystal X-ray diffraction. The η⁵,κP-Cp−P tethered complex [{(η5,κP-C₅Me₄CH₂C₆F₄-2-P(C₆F₅)CH₂P(C₆F₅)₂}RhCl₂] (9), in which only one phosphorus is coordinated to the rhodium, was prepared by thermolysis of a slurry of [Cp*RhCl(μ-Cl)]₂ and 2 and was structurally characterized by single-crystal X-ray diffraction. The tethering occurs by intramolecular dehydrofluorinative coupling of the η⁵-pentamethylcyclopentadienyl ligand and κP,κP-coordinated 2. The geometric changes that occur on tethering force dissociation of one of the phosphorus atoms. The effects of introducing phosphine ligands to the coordination sphere of piano stool hydrogen transfer catalysts have been studied. The complexes of fluorinated phosphine complexes are found to transfer hydrogen at rates that compare favorably with leading catalysts, particularly when the phosphine and cyclopentadienyl functionalities are tethered. The highly chelating η⁵,κP,κL-Cp−PP complex [(η⁵,κP,κP-C₅Me₄CH₂-2-C₅F₃N-4-PPhCH₂CH₂PPh₂)RhCl]BF₄ (1) was found to outperform all other complexes tested. The mechanism of hydrogen transfer catalyzed by piano stool phosphine complexes is discussed with reference to the trends in activity observed.

year: 2007

title: Eco-centric success: Stakeholder approaches to sustainable performance via green improvisation behavior and environmental orientation in the hotel industry

authors: Murtaza, Syed Hussain

subjects: environmental performance

abstract: This study delves into the relationship between green improvisational behavior (GIB), environmental orientation (EO), a green creative climate (GCC), and how they influence the environmental (EP) and social performance (SP) in the hotel industry. Through the perspective of stakeholder theory, the study examines how these factors work together to cultivate an atmosphere. The data was carefully collected through surveys at Pearl Continental Hotels & Resorts branches, a known chain of luxury hotels in Pakistan. Using Structural Equation Modeling for analysis, the study reveals insights for the hospitality industry in promoting a culture that encourages innovative and sustainable practices through environmentally friendly actions. By understanding what drives the development of an environment, hotels can create an organizational culture that supports eco-friendly initiatives. Additionally, this research contributes to existing knowledge by investigating the role of focus in effectively implementing and utilizing practices that promote a green creative climate for improved environmental and social performance within the hotel industry. The results provide implications for practices within hotels and offer theoretical perspectives on the factors driving sustainability efforts in this sector.

text: Eco-centric success: Stakeholder approaches to sustainable performance via green improvisation behavior and environmental orientation in the hotel industry This study delves into the relationship between green improvisational behavior (GIB), environmental orientation (EO), a green creative climate (GCC), and how they influence the environmental (EP) and social performance (SP) in the hotel industry. Through the perspective of stakeholder theory, the study examines how these factors work together to cultivate an atmosphere. The data was carefully collected through surveys at Pearl Continental Hotels & Resorts branches, a known chain of luxury hotels in Pakistan. Using Structural Equation Modeling for analysis, the study reveals insights for the hospitality industry in promoting a culture that encourages innovative and sustainable practices through environmentally friendly actions. By understanding what drives the development of an environment, hotels can create an organizational culture that supports eco-friendly initiatives. Additionally, this research contributes to existing knowledge by investigating the role of focus in effectively implementing and utilizing practices that promote a green creative climate for improved environmental and social performance within the hotel industry. The results provide implications for practices within hotels and offer theoretical perspectives on the factors driving sustainability efforts in this sector.

year: 2024

title: Fanning the divine spark: Gaining understandings of micro-interactions in New Zealand classrooms

authors: Eley, Elizabeth Martha Ann

subjects: micro-interactions

abstract: New Zealand’s Treaty of Waitangi was signed by representatives of Iwi Māori (Indigenous tribal groups) and the British Crown.  Inherent in the heritages of both signatory groups is the ontological positioning that children are born of greatness; carriers of the divine spark from Tama-nui-te-rā (the central sun) and created in the image of God.  Almost all New Zealand children attend school.  For some, their ongoing classroom experiences with educators fans their divine spark and works towards the realisation of their innate potential.  For others, schooling is not a positive experience and their divine spark may be neither recognised nor celebrated.  

This research explores the relationships and pedagogical practices that underpin the classroom micro-interactions experienced by children.  Children’s schooling experience is made up of small interactions in classrooms that are situated in the social, political and legal contexts of schooling.  Therefore, this research applies both a centripetal and a centrifugal examination of the macro and micro contexts of classroom interactions.  

In examining the macro-context, ontological views of the child and the theoretical frameworks that guide pedagogy are considered.  The Education Acts governing New Zealand schooling have successively contained an ontological contradiction that enforces both a factory model as the preferred means of schooling for New Zealand and a requirement to honour the Treaty of Waitangi, including the worldviews of both signatories.  I conclude that educators within the compulsory schooling sector are not provided with specific guidance on how to navigate these contradictory worldviews.  Neither ontological views of how children are perceived within the system, nor theoretical frameworks that could and should inform views of knowledge and how learning occurs, are made explicit for educators.  

At the micro-context level, relationships and pedagogical practices are explored through case studies in three different New Zealand classrooms.  In each case, from video-recordings of classroom interactions, critical incidents were extracted and used to support interviews with participating teachers, students, parents and members of the wider school community.  Employing culturally responsive research methodologies, the interactions with participants were relational and dialogic.  The research found that classroom micro-interactions are pervasive and complex.  All participants, students, teachers and whānau, draw from the knowledge, understandings and positionings of the individual’s own cultural toolkits in classroom interactions.  Their cultural toolkits contain a range of factors to support learning, all of which were necessary and interdependent.  

The thesis calls for all children to receive an education that fans their inherent divine spark.  While this experience is not yet the case for all, there is opportunity in the rhetoric and structures already within New Zealand’s education system for this to occur.  Some schools and communities have begun to successfully challenge and address the prevailing theoretical and pedagogical status quo.  Therefore, there is reason for radical hope for a system-wide fanning of the divine spark in every child.

text: Fanning the divine spark: Gaining understandings of micro-interactions in New Zealand classrooms New Zealand’s Treaty of Waitangi was signed by representatives of Iwi Māori (Indigenous tribal groups) and the British Crown.  Inherent in the heritages of both signatory groups is the ontological positioning that children are born of greatness; carriers of the divine spark from Tama-nui-te-rā (the central sun) and created in the image of God.  Almost all New Zealand children attend school.  For some, their ongoing classroom experiences with educators fans their divine spark and works towards the realisation of their innate potential.  For others, schooling is not a positive experience and their divine spark may be neither recognised nor celebrated.  

This research explores the relationships and pedagogical practices that underpin the classroom micro-interactions experienced by children.  Children’s schooling experience is made up of small interactions in classrooms that are situated in the social, political and legal contexts of schooling.  Therefore, this research applies both a centripetal and a centrifugal examination of the macro and micro contexts of classroom interactions.  

In examining the macro-context, ontological views of the child and the theoretical frameworks that guide pedagogy are considered.  The Education Acts governing New Zealand schooling have successively contained an ontological contradiction that enforces both a factory model as the preferred means of schooling for New Zealand and a requirement to honour the Treaty of Waitangi, including the worldviews of both signatories.  I conclude that educators within the compulsory schooling sector are not provided with specific guidance on how to navigate these contradictory worldviews.  Neither ontological views of how children are perceived within the system, nor theoretical frameworks that could and should inform views of knowledge and how learning occurs, are made explicit for educators.  

At the micro-context level, relationships and pedagogical practices are explored through case studies in three different New Zealand classrooms.  In each case, from video-recordings of classroom interactions, critical incidents were extracted and used to support interviews with participating teachers, students, parents and members of the wider school community.  Employing culturally responsive research methodologies, the interactions with participants were relational and dialogic.  The research found that classroom micro-interactions are pervasive and complex.  All participants, students, teachers and whānau, draw from the knowledge, understandings and positionings of the individual’s own cultural toolkits in classroom interactions.  Their cultural toolkits contain a range of factors to support learning, all of which were necessary and interdependent.  

The thesis calls for all children to receive an education that fans their inherent divine spark.  While this experience is not yet the case for all, there is opportunity in the rhetoric and structures already within New Zealand’s education system for this to occur.  Some schools and communities have begun to successfully challenge and address the prevailing theoretical and pedagogical status quo.  Therefore, there is reason for radical hope for a system-wide fanning of the divine spark in every child.

year: 2020