title: 1,2-Bis{(pentafluorophenyl)phenylphosphino}ethane:  A Probe for Configurational Stability in Three-Legged Piano Stool Complexes

authors: Nieuwenhuyzen, Mark

subjects: chemistry

abstract: The pentafluorophenyl-substituted diphosphine (C₆F₅)PhPCH₂CH₂PPh(C₆F₅) has been prepared, as a 1:1.7 mixture of rac (1a) and meso (1b) isomers, in four steps from dppe. The reaction between [Cp*RhCl(μ-Cl)]2 and 1 in the presence of tetrafluoroborate yielded a mixture of racemic diastereoisomers of [Cp*RhCl(κP,κP-1a)][BF₄] (4a•BF₄) and trans and cis isomers of [Cp*RhCl(κP,κP-1b)][BF₄] (4b•BF₄ and 4c•BF₄, respectively). On addition of Proton Sponge, 4a and 4c, in which at least one pentafluorophenyl group is close to the pentamethylcyclopentadienyl ligand, underwent rapid dehydrofluorinative carbon−carbon coupling giving trans- and cis-[{η⁵,κP,κP-C₅Me₄CH₂C₆F₄-2-PPhCH₂CH₂PPh(C₆F₅)}RhCl]⁺ (5 and 6), respectively. The latter underwent further dehydrofluorinative carbon−carbon coupling to give two isomers of [{η⁵,κP,κP-C₅Me₃[CH₂C₆F₄-2-PPhCH₂]₂}RhCl]+ (7). Isomerization of 4b to 4c was observed in chloroform and dimethlysulfoxide. Neither isomerization of 4a to 4b or 4c nor isomerization of 5 to 6 was observed at ambient or elevated temperature in dimethyl sulfoxide. The results provide the first evidence that complexes of η⁵,κP,κL-cyclopentadienyl-phosphine-donor ligands are configurationally stable at high temperature.

text: 1,2-Bis{(pentafluorophenyl)phenylphosphino}ethane:  A Probe for Configurational Stability in Three-Legged Piano Stool Complexes The pentafluorophenyl-substituted diphosphine (C₆F₅)PhPCH₂CH₂PPh(C₆F₅) has been prepared, as a 1:1.7 mixture of rac (1a) and meso (1b) isomers, in four steps from dppe. The reaction between [Cp*RhCl(μ-Cl)]2 and 1 in the presence of tetrafluoroborate yielded a mixture of racemic diastereoisomers of [Cp*RhCl(κP,κP-1a)][BF₄] (4a•BF₄) and trans and cis isomers of [Cp*RhCl(κP,κP-1b)][BF₄] (4b•BF₄ and 4c•BF₄, respectively). On addition of Proton Sponge, 4a and 4c, in which at least one pentafluorophenyl group is close to the pentamethylcyclopentadienyl ligand, underwent rapid dehydrofluorinative carbon−carbon coupling giving trans- and cis-[{η⁵,κP,κP-C₅Me₄CH₂C₆F₄-2-PPhCH₂CH₂PPh(C₆F₅)}RhCl]⁺ (5 and 6), respectively. The latter underwent further dehydrofluorinative carbon−carbon coupling to give two isomers of [{η⁵,κP,κP-C₅Me₃[CH₂C₆F₄-2-PPhCH₂]₂}RhCl]+ (7). Isomerization of 4b to 4c was observed in chloroform and dimethlysulfoxide. Neither isomerization of 4a to 4b or 4c nor isomerization of 5 to 6 was observed at ambient or elevated temperature in dimethyl sulfoxide. The results provide the first evidence that complexes of η⁵,κP,κL-cyclopentadienyl-phosphine-donor ligands are configurationally stable at high temperature.

year: 2006

title: Managing work-family conflict: Exploring individual and organisational options

authors: Haar, Jarrod M.

subjects: work-family conflict

abstract: The current work-family conflict literature often fails to examine how employees attempt to manage conflict. This study of 203 government workers examined individual options (e.g. hiring domestic help) and organisational options (e.g. use of flexitime) as predictors of work-family conflict. Of the individual options, help from family and relatives, and the use of domestic services were positively associated with work-family conflict, while time spent on self was negatively linked. Use of domestic services and stress reduction techniques were positively associated with family-work conflict, while time spent on self was negatively linked. Of the organizational options, use of the childcare subsidy was positively associated with work-family conflict, while use of unpaid leave was found to be negatively linked with work-family conflict. Use of unpaid leave was also negatively linked to family-work conflict, while use of flexitime was positively associated. Overall, findings indicate individual and organizational options are more likely to increase rather than decrease conflict suggesting a reaction to conflict rather than a buffer.

text: Managing work-family conflict: Exploring individual and organisational options The current work-family conflict literature often fails to examine how employees attempt to manage conflict. This study of 203 government workers examined individual options (e.g. hiring domestic help) and organisational options (e.g. use of flexitime) as predictors of work-family conflict. Of the individual options, help from family and relatives, and the use of domestic services were positively associated with work-family conflict, while time spent on self was negatively linked. Use of domestic services and stress reduction techniques were positively associated with family-work conflict, while time spent on self was negatively linked. Of the organizational options, use of the childcare subsidy was positively associated with work-family conflict, while use of unpaid leave was found to be negatively linked with work-family conflict. Use of unpaid leave was also negatively linked to family-work conflict, while use of flexitime was positively associated. Overall, findings indicate individual and organizational options are more likely to increase rather than decrease conflict suggesting a reaction to conflict rather than a buffer.

year: 2009

title: Racism and Employment: A Narrative Review of Aotearoa New Zealand and International Qualitative Studies

authors: Tan, Kyle K. H.

abstract: In Aotearoa New Zealand, employment inequities exist for minoritised ethnic groups (Māori, Pasifika, Asian, racialised migrants and refugees) in the forms of barriers to employment, occupation inequities, differences in promotion to leadership roles, ethnic pay gaps and discriminatory experiences at workplaces. In this review, we compiled Aotearoa qualitative studies to depict the dynamics of racism alongside other intersectional forms of prejudices that disadvantage the employment processes and career progression of minoritised ethnicities. Literature gaps in Aotearoa research were identified through reviewing international literature published between 2016 and 2021. Reviewed Aotearoa studies were categorised into three themes: unemployment and underemployment, workplace discrimination, and strategies for navigating racism. Drawing upon a framework that recognises racialised processes as spanning across micro- (individual), meso- (organisational) and macro- (institutional) levels, we found most Aotearoa studies analysing racism in the workplace focus on micro-level experiences. Compared with international literature, research in Aotearoa has yet to consider the roles of organisations and technologies as racialised structures that engender employment inequities, and the interaction of individuals in response to meso- and macro-structures that build on settler colonialism and racism. Our review echoes the call of Aotearoa scholars to name racism as the overarching oppressive mechanism embedded within organisations and to use anti-racism praxes such as te Tiriti o Waitangi as a way forward to promote employment equity.

text: Racism and Employment: A Narrative Review of Aotearoa New Zealand and International Qualitative Studies In Aotearoa New Zealand, employment inequities exist for minoritised ethnic groups (Māori, Pasifika, Asian, racialised migrants and refugees) in the forms of barriers to employment, occupation inequities, differences in promotion to leadership roles, ethnic pay gaps and discriminatory experiences at workplaces. In this review, we compiled Aotearoa qualitative studies to depict the dynamics of racism alongside other intersectional forms of prejudices that disadvantage the employment processes and career progression of minoritised ethnicities. Literature gaps in Aotearoa research were identified through reviewing international literature published between 2016 and 2021. Reviewed Aotearoa studies were categorised into three themes: unemployment and underemployment, workplace discrimination, and strategies for navigating racism. Drawing upon a framework that recognises racialised processes as spanning across micro- (individual), meso- (organisational) and macro- (institutional) levels, we found most Aotearoa studies analysing racism in the workplace focus on micro-level experiences. Compared with international literature, research in Aotearoa has yet to consider the roles of organisations and technologies as racialised structures that engender employment inequities, and the interaction of individuals in response to meso- and macro-structures that build on settler colonialism and racism. Our review echoes the call of Aotearoa scholars to name racism as the overarching oppressive mechanism embedded within organisations and to use anti-racism praxes such as te Tiriti o Waitangi as a way forward to promote employment equity.

year: 2024-01-01