title: N-Heterocyclic carbene gold(I) and silver(I) adducts of [Pt₂(μ-S)₂(PPh₃)₄]

authors: Henderson, William

subjects: platinum complexes

abstract: Reaction of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt₂(μ-S)₂(PPh₃)₄] that contain NHC ligands, namely [Pt₂(μ-S) ₂ (PPh₃)₄AuL]⁺ (L = IPr, IMes) and [Pt₂(μ-S)₂(PPh₃)₄AgIMes]⁺. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt₂(μ-S)₂(PPh₃)₄]  with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph₃PAuCl, which undergoes double addition giving [Pt₂(μ-SAuPPh₃)₂(PPh₃)₄]²⁺. The X-ray structure of [Pt₂(μ-S) ₂(PPh₃)₄AuIPr]PF₆ was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr⁺ moiety.

text: N-Heterocyclic carbene gold(I) and silver(I) adducts of [Pt₂(μ-S)₂(PPh₃)₄] Reaction of the metalloligand [Pt₂(μ-S)₂(PPh₃)₄] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt₂(μ-S)₂(PPh₃)₄] that contain NHC ligands, namely [Pt₂(μ-S) ₂ (PPh₃)₄AuL]⁺ (L = IPr, IMes) and [Pt₂(μ-S)₂(PPh₃)₄AgIMes]⁺. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt₂(μ-S)₂(PPh₃)₄]  with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph₃PAuCl, which undergoes double addition giving [Pt₂(μ-SAuPPh₃)₂(PPh₃)₄]²⁺. The X-ray structure of [Pt₂(μ-S) ₂(PPh₃)₄AuIPr]PF₆ was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr⁺ moiety.

year: 2011-11-30

title: PBRF on the horizon

authors: Smith, Ron C.

subjects: PBRF

abstract: New Zealand universities spend a great deal of time and money evaluating the research outputs of their staff in the cause of Performance Based Research Funding (PBRF).  This time and money is wasted since the assumptions that lie behind this process are fatally flawed and the results are neither valid nor fair.  Additionally PBRF is inconsistent with the universities’ obligations to be ‘critic and conscience’ for society and to scholarship, itself.  The paper argues that no further assessments of this kind should be undertaken.

text: PBRF on the horizon New Zealand universities spend a great deal of time and money evaluating the research outputs of their staff in the cause of Performance Based Research Funding (PBRF).  This time and money is wasted since the assumptions that lie behind this process are fatally flawed and the results are neither valid nor fair.  Additionally PBRF is inconsistent with the universities’ obligations to be ‘critic and conscience’ for society and to scholarship, itself.  The paper argues that no further assessments of this kind should be undertaken.

year: 2008-09-13

title: Role of tephra in dating Polynesian settlement and impact, New Zealand

authors: Lowe, David J.

subjects: tephrochronology

abstract: Tephrochronology in its original sense is the use of tephra layers as time-stratigraphic marker beds to establish numerical or relative ages (Lowe and Hunt, 2001). Tephra layers have been described and studied in New Zealand for more than 160 years (the German naturalist and surgeon Ernst Dieffenbach described ‘recognizable’ tephra sections in his 1843 book Travels in New Zealand), and the first isopach map, showing fallout from the deadly plinian basaltic eruption of Mt Tarawera on 10 June 1886, was published in 1888 (Lowe, 1990; Lowe et al., 2002). More recently, a wide range of tephra-related paleoenvironmental research has been undertaken (e.g., Lowe and Newnham, 1999; Newnham and Lowe, 1999; Newnham et al., 1999, 2004; Shane, 2000), including new advances in the role of tephra in linking and dating sites containing evidence for abrupt climatic change (e.g., Newnham and Lowe, 2000; Newnham et al., 2003). Here we focus on the use of tephrochronology in dating the arrival and impacts of the first humans in New Zealand, a difficult problem for which this technique has proven to be of critical importance.

text: Role of tephra in dating Polynesian settlement and impact, New Zealand Tephrochronology in its original sense is the use of tephra layers as time-stratigraphic marker beds to establish numerical or relative ages (Lowe and Hunt, 2001). Tephra layers have been described and studied in New Zealand for more than 160 years (the German naturalist and surgeon Ernst Dieffenbach described ‘recognizable’ tephra sections in his 1843 book Travels in New Zealand), and the first isopach map, showing fallout from the deadly plinian basaltic eruption of Mt Tarawera on 10 June 1886, was published in 1888 (Lowe, 1990; Lowe et al., 2002). More recently, a wide range of tephra-related paleoenvironmental research has been undertaken (e.g., Lowe and Newnham, 1999; Newnham and Lowe, 1999; Newnham et al., 1999, 2004; Shane, 2000), including new advances in the role of tephra in linking and dating sites containing evidence for abrupt climatic change (e.g., Newnham and Lowe, 2000; Newnham et al., 2003). Here we focus on the use of tephrochronology in dating the arrival and impacts of the first humans in New Zealand, a difficult problem for which this technique has proven to be of critical importance.

year: 2004