title: An investigation of the coordination chemistry of N,N`-disubstituted sulfonylthiourea ligands with d⁶ and d⁸ transition metal centres.

authors: Risi, Matthew

abstract: The coordination chemistry of both square-planar and piano-stool metal complexes derived from an array of disubstituted sulfonylthiourea ligands with the d⁸ and d⁶ transition metal centres of nickel(II), palladium(II), platinum(II), gold(III) and ruthenium(II) was investigated. It was found that these ligands coordinate to the metal centre through both the S and N atoms of the thiourea moiety in a bidentate fashion, which is reminiscent of the coordination chemistry of traditional thiourea complexes. Square-planar d⁸ metal complexes derived from sulfonylthioureas were characterised by both single crystal XRD and ³¹P{¹H} NMR aided by ¹⁹⁵Pt coupling, to be in the distal isomer with no isomerisation detected. This is to say that the non-coordinated nitrogen atom of the core thiourea bears the sulfonyl group and is positioned away from the metal centre. This is in contrast to the coordination observed for the analogous acylthiourea complexes which tend to favour a bidentate S and O coordination mode through the acyl oxygen. This indicates the coordination mode observed for square-planar sulfonylthiourea complexes more closely resembles that of unsubstituted thioureas. Interestingly, single crystal XRD analysis of the piano-stool ruthenium complexes reveals the sulfonylthiourea ligand coordinated to the ruthenium metal centre in the unexpected proximal isomer. Comparison of this structure to some analogous piano-stool acylthiourea complexes show extremely similar structure and coordination and may indicate piano-stool structures derived from sulfonylthioureas resemble those of acylthioureas which in-turn is similar to the coordination mode adopted by simple thioureas. Moreover, through monitoring of the observed decomposition of Ni(II) and Pd(II) sulfonylthiourea complexes by ESI-MS and ³¹P NMR and the attempted synthesis of monodentate Au(I) phosphine sulfonylthiourea complexes, it was discovered that these complexes have a tendency to form stable trinuclear aggregates of the formula [M₃S₂L₃]⁺ (L = bidentate chelating ligand). The formation of these sulfide complexes is theorised to be a result of a hydroxide induced S-C bond cleavage promoted by the electron withdrawing sulfonyl subsistent. This observation matches closely to the well-known ability of thioureas to act as a source of sulfide upon reactions with metal ions.

text: An investigation of the coordination chemistry of N,N`-disubstituted sulfonylthiourea ligands with d⁶ and d⁸ transition metal centres. The coordination chemistry of both square-planar and piano-stool metal complexes derived from an array of disubstituted sulfonylthiourea ligands with the d⁸ and d⁶ transition metal centres of nickel(II), palladium(II), platinum(II), gold(III) and ruthenium(II) was investigated. It was found that these ligands coordinate to the metal centre through both the S and N atoms of the thiourea moiety in a bidentate fashion, which is reminiscent of the coordination chemistry of traditional thiourea complexes. Square-planar d⁸ metal complexes derived from sulfonylthioureas were characterised by both single crystal XRD and ³¹P{¹H} NMR aided by ¹⁹⁵Pt coupling, to be in the distal isomer with no isomerisation detected. This is to say that the non-coordinated nitrogen atom of the core thiourea bears the sulfonyl group and is positioned away from the metal centre. This is in contrast to the coordination observed for the analogous acylthiourea complexes which tend to favour a bidentate S and O coordination mode through the acyl oxygen. This indicates the coordination mode observed for square-planar sulfonylthiourea complexes more closely resembles that of unsubstituted thioureas. Interestingly, single crystal XRD analysis of the piano-stool ruthenium complexes reveals the sulfonylthiourea ligand coordinated to the ruthenium metal centre in the unexpected proximal isomer. Comparison of this structure to some analogous piano-stool acylthiourea complexes show extremely similar structure and coordination and may indicate piano-stool structures derived from sulfonylthioureas resemble those of acylthioureas which in-turn is similar to the coordination mode adopted by simple thioureas. Moreover, through monitoring of the observed decomposition of Ni(II) and Pd(II) sulfonylthiourea complexes by ESI-MS and ³¹P NMR and the attempted synthesis of monodentate Au(I) phosphine sulfonylthiourea complexes, it was discovered that these complexes have a tendency to form stable trinuclear aggregates of the formula [M₃S₂L₃]⁺ (L = bidentate chelating ligand). The formation of these sulfide complexes is theorised to be a result of a hydroxide induced S-C bond cleavage promoted by the electron withdrawing sulfonyl subsistent. This observation matches closely to the well-known ability of thioureas to act as a source of sulfide upon reactions with metal ions.

year: 2020

title: The Relevance of the “h-” and “g-” Index to Economics in the Context of A Nation-Wide Research Evaluation Scheme: The New Zealand Case

authors: Anderson, David L.

subjects: “h-” and “g-”indexes

abstract: The purpose of this paper is to explore the relevance of the citation-based “h-” and “g-” indexes as a means for measuring research output in economics. This study is unique in that it is the first to utilise the “h-” and “g-”indexes in the context of a time-limited evaluation period and to provide comprehensive coverage of all academic economists in all university-based economics departments within a nation state. For illustration purposes, we have selected the New Zealand's Performance-Based Research Fund (PBRF) as our evaluation scheme. To provide a frame of reference for “h-” and “g-”index-output measures, we have also estimated research output using a number of journal-based weighting schemes. In general, our findings suggest that “h-” and “g-”index scores are strongly associated with low-powered journal ranking schemes and weakly associated with high powered journal weighting schemes. More specifically, we found the “h-” and “g-”indexes to suffer from a lack of differentiation: for example, 52 per cent of all participants received a score of zero under both measures, and 92 and 89 per cent received scores of two or less under “h-” and “g-” respectively. Overall, our findings suggest that “h-” and “g-”indexes should not be incorporated into a PBRF-like framework.

text: The Relevance of the “h-” and “g-” Index to Economics in the Context of A Nation-Wide Research Evaluation Scheme: The New Zealand Case The purpose of this paper is to explore the relevance of the citation-based “h-” and “g-” indexes as a means for measuring research output in economics. This study is unique in that it is the first to utilise the “h-” and “g-”indexes in the context of a time-limited evaluation period and to provide comprehensive coverage of all academic economists in all university-based economics departments within a nation state. For illustration purposes, we have selected the New Zealand's Performance-Based Research Fund (PBRF) as our evaluation scheme. To provide a frame of reference for “h-” and “g-”index-output measures, we have also estimated research output using a number of journal-based weighting schemes. In general, our findings suggest that “h-” and “g-”index scores are strongly associated with low-powered journal ranking schemes and weakly associated with high powered journal weighting schemes. More specifically, we found the “h-” and “g-”indexes to suffer from a lack of differentiation: for example, 52 per cent of all participants received a score of zero under both measures, and 92 and 89 per cent received scores of two or less under “h-” and “g-” respectively. Overall, our findings suggest that “h-” and “g-”indexes should not be incorporated into a PBRF-like framework.

year: 2013

title: Romeo and Tusi: An eclectically musical Samoan/Māori Romeo and Juliet from Aotearoa/New Zealand

authors: Houlahan, Mark

subjects: Romeo and Tusi

abstract: Is there a distinctive New Zealand Shakespeare? What ‘new’ approaches to Shakespeare have originated from New Zealand? This article explores the issue by contextualising a version of Romeo and Juliet staged successfully throughout New Zealand in the late 1990s. The production is set against the background of the history of Shakespeare in New Zealand, which goes back to the arrival of Captain Cook on the Endeavour in 1769.

Pacific Underground's Romeo and Tusi sought a looser and more populist kind of Shakespeare performance. They used the conceit of rehearsing the play at high school, where a Māori Romeo and a Samoan Juliet cross community boundaries. Drawing on several music genres, and performing outdoors, they generated a Shakespeare that audiences from a diverse range of ethnic and cultural communities could enjoy.

text: Romeo and Tusi: An eclectically musical Samoan/Māori Romeo and Juliet from Aotearoa/New Zealand Is there a distinctive New Zealand Shakespeare? What ‘new’ approaches to Shakespeare have originated from New Zealand? This article explores the issue by contextualising a version of Romeo and Juliet staged successfully throughout New Zealand in the late 1990s. The production is set against the background of the history of Shakespeare in New Zealand, which goes back to the arrival of Captain Cook on the Endeavour in 1769.

Pacific Underground's Romeo and Tusi sought a looser and more populist kind of Shakespeare performance. They used the conceit of rehearsing the play at high school, where a Māori Romeo and a Samoan Juliet cross community boundaries. Drawing on several music genres, and performing outdoors, they generated a Shakespeare that audiences from a diverse range of ethnic and cultural communities could enjoy.

year: 2009