title: Ligand exchange reactions of [Re₂(μ-OR)₃(CO)₆]⁻(R = H, Me) with sulfur, selenium, phosphorus and nitrogen donor ligands, investigated by electrospray mass spectrometry

authors: Jiang, Chenghua

subjects: chemistry

abstract: Negative-ion electrospray mass spectrometry has been used to investigate the reactions of the dinuclear rhenium aggregates [Re₂(μ-OH)₃(CO)₆]⁻ 1 and [Re₂(μ-OMe)₃(CO)₆]⁻ 2 with a range of thiols, benzeneselenol, and some other sulfur-, phosphorus- and nitrogen-based ligands. Typically up to three of the hydroxo ligands are replaced by simple thiolates, giving the series of species [Re₂(OH)₂(SR)(CO)₆]⁻, [Re₂(OH)(SR)₂(CO)₆]⁻, and [Re₂(SR)₃(CO)₆]⁻. Similarly, reaction of 1 with H₂S gives the species [Re₂(μ-SH)₃(CO)₆]⁻, which undergoes an analogous fragmentation process to [Re₂(μ-OH)₃(CO)₆]⁻, at high cone voltages, by loss of H₂S and formation of [Re₂(S)(SH)(CO)₆]⁻. With ligands which are good chelating agents (such as dithiocarbamates R₂NCS₂⁻, and thiosalicylic acid, HSC₆H₄CO₂H) initial substitution of one or two OH groups readily occurs, but on standing the dimer is cleaved giving [Re(S₂CNR₂)₂(CO)₃]⁻ and [Re(SC₆H₄CO₂)(CO)₃]⁻. The different reactivities of the dithiol reagents benzene-1,2- and benzene-1,4-dimethanethiol towards 1 are also described. Complex 1 also reacts with aniline, and with primary (but not secondary) amides RC(O)NH₂, giving monosubstituted species [Re₂(OH)₂(NHPh)(CO)₆]⁻ and [Re₂(OH)₂{NHC(O)R}(CO)₆]⁻ respectively. The reactions with adenine and thymine, and with the inorganic anions thiocyanate and thiosulfate, are also described.

text: Ligand exchange reactions of [Re₂(μ-OR)₃(CO)₆]⁻(R = H, Me) with sulfur, selenium, phosphorus and nitrogen donor ligands, investigated by electrospray mass spectrometry Negative-ion electrospray mass spectrometry has been used to investigate the reactions of the dinuclear rhenium aggregates [Re₂(μ-OH)₃(CO)₆]⁻ 1 and [Re₂(μ-OMe)₃(CO)₆]⁻ 2 with a range of thiols, benzeneselenol, and some other sulfur-, phosphorus- and nitrogen-based ligands. Typically up to three of the hydroxo ligands are replaced by simple thiolates, giving the series of species [Re₂(OH)₂(SR)(CO)₆]⁻, [Re₂(OH)(SR)₂(CO)₆]⁻, and [Re₂(SR)₃(CO)₆]⁻. Similarly, reaction of 1 with H₂S gives the species [Re₂(μ-SH)₃(CO)₆]⁻, which undergoes an analogous fragmentation process to [Re₂(μ-OH)₃(CO)₆]⁻, at high cone voltages, by loss of H₂S and formation of [Re₂(S)(SH)(CO)₆]⁻. With ligands which are good chelating agents (such as dithiocarbamates R₂NCS₂⁻, and thiosalicylic acid, HSC₆H₄CO₂H) initial substitution of one or two OH groups readily occurs, but on standing the dimer is cleaved giving [Re(S₂CNR₂)₂(CO)₃]⁻ and [Re(SC₆H₄CO₂)(CO)₃]⁻. The different reactivities of the dithiol reagents benzene-1,2- and benzene-1,4-dimethanethiol towards 1 are also described. Complex 1 also reacts with aniline, and with primary (but not secondary) amides RC(O)NH₂, giving monosubstituted species [Re₂(OH)₂(NHPh)(CO)₆]⁻ and [Re₂(OH)₂{NHC(O)R}(CO)₆]⁻ respectively. The reactions with adenine and thymine, and with the inorganic anions thiocyanate and thiosulfate, are also described.

year: 2000

title: Refining personal and social presence in virtual meetings

authors: Dean, Jesse

subjects: virtual meeting

abstract: Virtual worlds show promise for conducting meetings and conferences without the need for physical travel. Current experience suggests the major limitation to the more widespread adoption and acceptance of virtual conferences is the failure of existing environments to provide a sense of immersion and engagement, or of ‘being there’. These limitations are largely related to the appearance and control of avatars, and to the absence of means to convey non-verbal cues of facial expression and body language. This paper reports on a study involving the use of a mass-market motion sensor (Kinect™) and the mapping of participant action in the real world to avatar behaviour in the virtual world. This is coupled with full-motion video representation of participant’s faces on their avatars to resolve both identity and facial expression issues. The outcomes of a small-group trial meeting based on this technology show a very positive reaction from participants, and the potential for further exploration of these concepts.

text: Refining personal and social presence in virtual meetings Virtual worlds show promise for conducting meetings and conferences without the need for physical travel. Current experience suggests the major limitation to the more widespread adoption and acceptance of virtual conferences is the failure of existing environments to provide a sense of immersion and engagement, or of ‘being there’. These limitations are largely related to the appearance and control of avatars, and to the absence of means to convey non-verbal cues of facial expression and body language. This paper reports on a study involving the use of a mass-market motion sensor (Kinect™) and the mapping of participant action in the real world to avatar behaviour in the virtual world. This is coupled with full-motion video representation of participant’s faces on their avatars to resolve both identity and facial expression issues. The outcomes of a small-group trial meeting based on this technology show a very positive reaction from participants, and the potential for further exploration of these concepts.

year: 2014

title: The gown and the korowai: Maori doctoral students and the spatial organization of academic knowledge

authors: Middleton, Sue

subjects: culture

abstract: This paper draws on 38 student interviews carried out in the course of the team research project Teaching and Learning in the Supervision of Māori Doctoral Students. Māori doctoral thesis work takes place in the intersections between the Māori (tribal) world of identifications and obligations, the organisational and epistemological configurations of academia, and the bureaucratic requirements of funding or employing bureaucracies. To explore how students accommodate cultural, academic and bureaucratic demands, we develop analytical tools combining three intellectual traditions: Māori educational theory, Bernstein’s sociology of the academy, and Lefebvre’s conceptual trilogy of perceived, conceived, and lived space.

text: The gown and the korowai: Maori doctoral students and the spatial organization of academic knowledge This paper draws on 38 student interviews carried out in the course of the team research project Teaching and Learning in the Supervision of Māori Doctoral Students. Māori doctoral thesis work takes place in the intersections between the Māori (tribal) world of identifications and obligations, the organisational and epistemological configurations of academia, and the bureaucratic requirements of funding or employing bureaucracies. To explore how students accommodate cultural, academic and bureaucratic demands, we develop analytical tools combining three intellectual traditions: Māori educational theory, Bernstein’s sociology of the academy, and Lefebvre’s conceptual trilogy of perceived, conceived, and lived space.

year: 2009