title: Electrospray mass spectrometric analysis of transition metal carbonyl clusters

authors: Evans, Cameron

subjects: Transition metal complexes Spectra

abstract: ﻿A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. 
An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. 
ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. 
The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. 
ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. 
The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4].
 The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. A structure determination of [PPN][Mo(C0)3(ri5-CsHs)] is also reported.

text: Electrospray mass spectrometric analysis of transition metal carbonyl clusters ﻿A key objective of this thesis was to develop Electrospray (Ionisation) Mass Spectrometry (ESMS) within organometallic chemistry, specifically as a technique for investigating transition metal carbonyl cluster chemistry. 
An initial survey of air-sensitive high-nuclearity rhodium and nickel clusters, such as [Rh9As(C0)21f and [H2Ni!2(CO)iif, demonstrated the usefulness of ESMS for characterisation. 
ESMS was applied to monitoring the reactions of ~-E[M2(CO)xh [E = Si, Ge, Sn; M = Co (x = 7), Fe (x = 8)] with anionic transition metal carbonyl reagents. Analysis of the reaction between ~-Ge[Coi(C0)7h and [Co(C0)4r revealed the inter-conversion processes between previously isolated clusters, and was crucial in identifying the unheralded [Co10Gei(C0)24f product. Conditions for optimal yields of this anion were established and the cluster subsequently isolated and structurally characterised (below). The core structure of [Co10Ge2(C0)24f is unprecedented and is discussed in terms of electron-counting theories. 
The analogous reaction with µ4-Si[Co2(C0)7h gave indication of novel cluster products. These included [Co5Si(C0)16r, [Co9Si(C0h2r and [Co7Si(COh1L as well as the previously reported [Co9Si(CO)iif. Reactions with [Fe2(CO)sf, [HFe(C0)4r, [Fe(C0)3(NO)L [Mn(CO)sr and [Mo(C0)3(ri5-CsHs)r were less straight-forward, but again led to the detection of new clusters. 
ESMS analysis confirmed the unusual result that [Co14N3(C0h6]3 • is the only highnuclearity thermolysis product of [Co6N(C0)15r. The specificity of the reaction can only be established by ESMS since the technique precludes the existence of any other significant ionic products. 
The reaction between PCls and [Co(C0)4r gave the known [CoJ>(CO)i6r and [Co9P(C0)21f- clusters while the analogous reaction with AsCh produced three novel cobalt arsenido species, [Co~s(C0)16L [Co1As2(C0)17r and [Co9As2(C0)21r. The previously reported [Co4Sb2(C0)11r and novel [CosSb2(C0)14r clusters were identified in the reaction between SbCh and [Co(C0)4].
 The synthesis and characterisation of a series of Co4(1-4-ER)2(C0)11 clusters are described. The dimethylamino functionalised examples, Co4(1-4-ECi#4NMe2)2(C0)11 E = Si, Ge, were characterised by ESMS as their [M+Ht ions. The Co4(J.4-SiR)2(C0)11 [R = Ph, CJliOMe, (CH2)30Me] clusters underwent facile substitution with isonitrile and phosphite reagents but equivalent phosphine-substituted products were not observed by ESMS. Isonitrile-substituted clusters (n > 2) gave clear~ ions in their ES mass spectra arising from in situ oxidation. The novel Co4(1-4-SiC~OMe)2(C0)1(XyNC)4 cluster was structurally characterised (below). Linked clusters of the form [Co4(1-4- SiCJliR)(C0)11Si]2X [R = H, OMe; X = (CH2)s, CJii] were isolated, albeit in very low yield. An oligomeric -[XSiCo4(C0)11 Si]-0 species was tentatively identified. A new structural isomer of [CoFe3(C0)13r was characterised. The ligand arrangement for [NE4][CoFe3(C0)13] differs significantly from that of [PPN][C0Fe3(C0)13] and [NE4][C0Ru3(C0)13]. A structure determination of [PPN][Mo(C0)3(ri5-CsHs)] is also reported.

year: 2002

title: Errorless compliance training: Used by a researcher and teacher aides to increase compliance of children under five years of age in either the home or education setting

authors: Noorland, Jana Maree

subjects: Errorless Compliance Training

abstract: Errorless Compliance Training (ECT) was developed as a nonaversive alternative approach to traditional compliance training (Ducharme  Worling,1994; Ducharme, Popynick, Pontes,  Steele,1996). Experiment 1 aimed to see if this method could be used to increase the compliance of three children aged four, with two of the participants‟ treatments taking place in the family home and the third taking place in an early education setting. Results showed that all participants had increases in the level of compliance to specific requests. Child 1 and 3 completed all phases of the training and showed significant increases in compliance to Level 4 requests compared to that of the baseline data. Child 2 reached Phase 3 only, however, he still had significant increases in compliance in Phase 2 and 3 of the treatment. The results suggest that Errorless Compliance Training was successful in increasing compliance with these participants, who were four years of age, in an early education setting as well as in home settings. Experiment 2 aimed to increase compliance with two children in a primary school setting, by teaching the teacher aides working with the children Errorless Compliance Training following Ducharme‟s (1996) procedure. Replication of Ducharme‟s Errorless Compliance Training findings to increased compliance was not possible. A range of issues meant the Observational Probability Analyses were not completed in the time frame and treatment could not begin. Experiment 2‟s results suggest that Errorless Compliance Training may not be a treatment that can be easily implemented by teacher aides within the school setting. One reason for this is that the Observation Probability Analysis requires all requests to be delivered each session, which takes
ii
approximately two hours, therefore the sessions are not able to be completed within the time restraints of the teacher aides.

text: Errorless compliance training: Used by a researcher and teacher aides to increase compliance of children under five years of age in either the home or education setting Errorless Compliance Training (ECT) was developed as a nonaversive alternative approach to traditional compliance training (Ducharme  Worling,1994; Ducharme, Popynick, Pontes,  Steele,1996). Experiment 1 aimed to see if this method could be used to increase the compliance of three children aged four, with two of the participants‟ treatments taking place in the family home and the third taking place in an early education setting. Results showed that all participants had increases in the level of compliance to specific requests. Child 1 and 3 completed all phases of the training and showed significant increases in compliance to Level 4 requests compared to that of the baseline data. Child 2 reached Phase 3 only, however, he still had significant increases in compliance in Phase 2 and 3 of the treatment. The results suggest that Errorless Compliance Training was successful in increasing compliance with these participants, who were four years of age, in an early education setting as well as in home settings. Experiment 2 aimed to increase compliance with two children in a primary school setting, by teaching the teacher aides working with the children Errorless Compliance Training following Ducharme‟s (1996) procedure. Replication of Ducharme‟s Errorless Compliance Training findings to increased compliance was not possible. A range of issues meant the Observational Probability Analyses were not completed in the time frame and treatment could not begin. Experiment 2‟s results suggest that Errorless Compliance Training may not be a treatment that can be easily implemented by teacher aides within the school setting. One reason for this is that the Observation Probability Analysis requires all requests to be delivered each session, which takes
ii
approximately two hours, therefore the sessions are not able to be completed within the time restraints of the teacher aides.

year: 2010

title: Kia whakatōmuri te haere whakamua: ‘I walk backwards into the future with my eyes fixed on my past’

authors: Rameka, Lesley Kay

subjects: Māori

abstract: This whakataukī or ‘proverb’ speaks to Māori perspectives of time, where the past, the present and the future are viewed as intertwined, and life as a continuous cosmic process. Within this continuous cosmic movement, time has no restrictions – it is both past and present. The past is central to and shapes both present and future identity. From this perspective, the individual carries their past into the future. The strength of carrying one’s past into the future is that ancestors are ever present, existing both within the spiritual realm and in the physical, alongside the living as well as within the living. This article explores Māori perspectives of the past and the models and inspiration they offer. In this way, it provides a critique of the practices in early childhood education, highlighting the importance of cultural concepts and practices, and discusses implications for both teaching and academic practice.

text: Kia whakatōmuri te haere whakamua: ‘I walk backwards into the future with my eyes fixed on my past’ This whakataukī or ‘proverb’ speaks to Māori perspectives of time, where the past, the present and the future are viewed as intertwined, and life as a continuous cosmic process. Within this continuous cosmic movement, time has no restrictions – it is both past and present. The past is central to and shapes both present and future identity. From this perspective, the individual carries their past into the future. The strength of carrying one’s past into the future is that ancestors are ever present, existing both within the spiritual realm and in the physical, alongside the living as well as within the living. This article explores Māori perspectives of the past and the models and inspiration they offer. In this way, it provides a critique of the practices in early childhood education, highlighting the importance of cultural concepts and practices, and discusses implications for both teaching and academic practice.

year: 2017