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: Guide to the nature and methods of analysis of the clay fraction of tephras from the South Auckland region, New Zealand.

authors: Lowe, David J.

abstract: The manual outlines some of the more common laboratory procedures available for qualitatively and quantitatively analysing the composition of the tephric clays, many of which are difficult to determine because of their short range order or 'amorphous' nature. Techniques described and assessed in terms of their rapidity and quantitativeness include XRD, IR, DTA, TEM and SEM, sodium fluoride reactivity, chemical dissolution analyses, and surface area measurements. No one technique alone produces a definitive clay fraction analysis of tephric deposits. -from Authors

text: Guide to the nature and methods of analysis of the clay fraction of tephras from the South Auckland region, New Zealand. The manual outlines some of the more common laboratory procedures available for qualitatively and quantitatively analysing the composition of the tephric clays, many of which are difficult to determine because of their short range order or 'amorphous' nature. Techniques described and assessed in terms of their rapidity and quantitativeness include XRD, IR, DTA, TEM and SEM, sodium fluoride reactivity, chemical dissolution analyses, and surface area measurements. No one technique alone produces a definitive clay fraction analysis of tephric deposits. -from Authors

year: 1983

title: Spot sampling of nutrient concentrations in the Puarenga catchment, Rotorua

authors: Abell, Jonathan Michael

subjects: New Zealand

abstract: The Centre for Biodiversity and Ecology Research was approached by Tūhourangi Tribal Authority for assistance with measuring water quality in streams in the Puarenga Stream catchment. Water sampling was subsequently undertaken on 18 July 2011 and samples were analysed to determine concentrations of total and dissolved fractions of nitrogen and phosphorus. 
Nitrogen and phosphorus are both essential plant nutrients which, when present in excess, can cause eutrophication and associated water quality decline of freshwaters. High concentrations of dissolved forms of nitrogen can also be toxic to aquatic organisms. Excessive nitrogen and phosphorus concentrations are typically the result of pollution due to human activities, although groundwater in the Central Volcanic Plateau region can have elevated concentrations of phosphorus arising from natural geological sources.
This report summarises the methods used, presents the results and places measured concentrations in context by drawing comparisons with both guideline and regional mean values.

text: Spot sampling of nutrient concentrations in the Puarenga catchment, Rotorua The Centre for Biodiversity and Ecology Research was approached by Tūhourangi Tribal Authority for assistance with measuring water quality in streams in the Puarenga Stream catchment. Water sampling was subsequently undertaken on 18 July 2011 and samples were analysed to determine concentrations of total and dissolved fractions of nitrogen and phosphorus. 
Nitrogen and phosphorus are both essential plant nutrients which, when present in excess, can cause eutrophication and associated water quality decline of freshwaters. High concentrations of dissolved forms of nitrogen can also be toxic to aquatic organisms. Excessive nitrogen and phosphorus concentrations are typically the result of pollution due to human activities, although groundwater in the Central Volcanic Plateau region can have elevated concentrations of phosphorus arising from natural geological sources.
This report summarises the methods used, presents the results and places measured concentrations in context by drawing comparisons with both guideline and regional mean values.

year: 2011-09