title: Preparation and reactions of some organic derivatives of manganese carbonyl compounds

authors: Cooney, Janine M.

abstract: New orthomanganated aryl ketones of type 1 (Figure 1) have been prepared, including some in which the donor ketone carbonyl group is incorporated into a fused ring. Analogous derivatives of benzoates and heteroaromatic carboxylic acid esters are also described, together with several orthorheniated compounds. Single crystal X-ray structure determinations of η²-5-(1,4-benzopyronyl)tetracarbonylmanganese (13) and η²-(4-acetyl-2,5-dimethylthien-3 yl) tetracarbonylrhenium (32) are reported.

Reactions of orthomanganated aryl ketones with SO₂ and with the electronically and structurally related cumulenes, N-sulfinylaniline (PhN=S=O), N-sulfinylbenzenesulfonamide (PhS(O)₂N=S=O) and the disulfonylsulfodiimide [PhS(O)₂N]₂S have been investigated. SO₂ inserts efficiently into the Mn-Cₐᵣᵧₗ bond of a range of orthomanganated ketones, to give the corresponding S-sulfinato complex e.g. (43) (Figure 1). The X-ray crystal structure of (43) was determined and it is the first reported example of a six-membered metallocycle incorporating an O, Mn and S atom. 

In contrast, reaction of PhN=S=O with a number of orthomanganated acetophenones led to the corresponding orthomanganated imines e.g. (38) (Figure 1). The structure of η²-3-chloro-2-[1-(N-phenylimino)ethyl]-phenyl-tetracarbonylmanganese (44) was determined by single crystal X-ray diffraction.

PhS(O)₂NSO and [PhS(O)₂N]₂S did not react with orthomanganated p-methoxyacetophenone (39) under similar conditions.

The palladium- and thermally-promoted coupling reactions of orthomanganated aryl ketones and esters with alkenes have been explored in detail.

In the presence of Pd(II), η²-(o-acetylaryl)tetracarbonylmanganese compounds undergo coupling reactions with methyl acrylate, methyl vinyl ketone, acrylonitrile, acrolein, vinyl acetate and allyl alcohol. The coupling reactions normally proceed in excellent yield and produce three main products, arylalkene, arylalkane and indene, the ratios of which vary with reaction conditions and substrate (Scheme 1; Path (I)).

Orthomercurated aryl ketones obtained via transmetalation of orthomanganated ketones with mercuric chloride allowed a comparison of the product distribution for Pd(II)-promoted methyl acrylate coupling of an orthomercurated precursor 4-acetyl-2,5-dimethylthien-3-ylmercury(II) chloride (112) and the corresponding orthomanganated precursor η²-(4-acetyl-2,5-dimethylthien-3-yl)tetracarbonylmanganese (41) under identical conditions. Cyclisation to give the indene-type product methyl 1,3,6- trimethyl-4H-cyclopenta[c]thiophene-5- carboxylate (53) (whose crystal structure is reported) was found to be much more strongly favoured in the Mn than the Hg case precluding the possibility that the only role of both replaced metals is in transmetalation with palladium prior to alkene coupling. This conclusion is supported by similar reactions with phosphite or phosphine derivatives of cyclomanganated aryl ketones e.g. (145), (146) (Figure 2), and by reactions of orthorheniated substrates e.g. (32) (Figure 2).

In the absence of Pd(II), alkenes were also found to insert efficiently into the Mn-Cₐᵣᵧₗ bond of orthomanganated ketones at ca 80 °C. In this case, the major products were found to be arylalkane, indene and a mixture of the diastereoisomeric indanols (Scheme 1; Path (II)). Arylalkene products were formed in very small or indetectable amounts. Possible reaction pathways for both the Pd(II) and the thermally initiated reactions are presented. 

Several sterically crowded 3-substituted orthomanganated esters and ketones were reacted with ICl to give the corresponding 2-iodo-3-substituted compounds (e.g. Equation 1). 3-Substituted 2-iodo esters formed via this route are of interest as potential precursors for the formation of 5-substituted 9-oxo-9H-xanthene-4 acetic acid (XAA) compounds, which exhibit antitumour activity.

text: Preparation and reactions of some organic derivatives of manganese carbonyl compounds New orthomanganated aryl ketones of type 1 (Figure 1) have been prepared, including some in which the donor ketone carbonyl group is incorporated into a fused ring. Analogous derivatives of benzoates and heteroaromatic carboxylic acid esters are also described, together with several orthorheniated compounds. Single crystal X-ray structure determinations of η²-5-(1,4-benzopyronyl)tetracarbonylmanganese (13) and η²-(4-acetyl-2,5-dimethylthien-3 yl) tetracarbonylrhenium (32) are reported.

Reactions of orthomanganated aryl ketones with SO₂ and with the electronically and structurally related cumulenes, N-sulfinylaniline (PhN=S=O), N-sulfinylbenzenesulfonamide (PhS(O)₂N=S=O) and the disulfonylsulfodiimide [PhS(O)₂N]₂S have been investigated. SO₂ inserts efficiently into the Mn-Cₐᵣᵧₗ bond of a range of orthomanganated ketones, to give the corresponding S-sulfinato complex e.g. (43) (Figure 1). The X-ray crystal structure of (43) was determined and it is the first reported example of a six-membered metallocycle incorporating an O, Mn and S atom. 

In contrast, reaction of PhN=S=O with a number of orthomanganated acetophenones led to the corresponding orthomanganated imines e.g. (38) (Figure 1). The structure of η²-3-chloro-2-[1-(N-phenylimino)ethyl]-phenyl-tetracarbonylmanganese (44) was determined by single crystal X-ray diffraction.

PhS(O)₂NSO and [PhS(O)₂N]₂S did not react with orthomanganated p-methoxyacetophenone (39) under similar conditions.

The palladium- and thermally-promoted coupling reactions of orthomanganated aryl ketones and esters with alkenes have been explored in detail.

In the presence of Pd(II), η²-(o-acetylaryl)tetracarbonylmanganese compounds undergo coupling reactions with methyl acrylate, methyl vinyl ketone, acrylonitrile, acrolein, vinyl acetate and allyl alcohol. The coupling reactions normally proceed in excellent yield and produce three main products, arylalkene, arylalkane and indene, the ratios of which vary with reaction conditions and substrate (Scheme 1; Path (I)).

Orthomercurated aryl ketones obtained via transmetalation of orthomanganated ketones with mercuric chloride allowed a comparison of the product distribution for Pd(II)-promoted methyl acrylate coupling of an orthomercurated precursor 4-acetyl-2,5-dimethylthien-3-ylmercury(II) chloride (112) and the corresponding orthomanganated precursor η²-(4-acetyl-2,5-dimethylthien-3-yl)tetracarbonylmanganese (41) under identical conditions. Cyclisation to give the indene-type product methyl 1,3,6- trimethyl-4H-cyclopenta[c]thiophene-5- carboxylate (53) (whose crystal structure is reported) was found to be much more strongly favoured in the Mn than the Hg case precluding the possibility that the only role of both replaced metals is in transmetalation with palladium prior to alkene coupling. This conclusion is supported by similar reactions with phosphite or phosphine derivatives of cyclomanganated aryl ketones e.g. (145), (146) (Figure 2), and by reactions of orthorheniated substrates e.g. (32) (Figure 2).

In the absence of Pd(II), alkenes were also found to insert efficiently into the Mn-Cₐᵣᵧₗ bond of orthomanganated ketones at ca 80 °C. In this case, the major products were found to be arylalkane, indene and a mixture of the diastereoisomeric indanols (Scheme 1; Path (II)). Arylalkene products were formed in very small or indetectable amounts. Possible reaction pathways for both the Pd(II) and the thermally initiated reactions are presented. 

Several sterically crowded 3-substituted orthomanganated esters and ketones were reacted with ICl to give the corresponding 2-iodo-3-substituted compounds (e.g. Equation 1). 3-Substituted 2-iodo esters formed via this route are of interest as potential precursors for the formation of 5-substituted 9-oxo-9H-xanthene-4 acetic acid (XAA) compounds, which exhibit antitumour activity.

year: 1994

title: Software frameworks for rural AI robotics

authors: Bashir, Faizan

abstract: Robotic Autonomous robotic systems intended for agricultural environments must operate under conditions of unreliable connectivity, limited infrastructure, and high environmental variability. These constraints present significant challenges for system architecture, communication design, and human– robot interaction. This thesis investigates these challenges through the design, analysis, and evaluation of Nicobot, a mobile agricultural research platform developed to explore software frameworks for rural AI robotics.   
The research focuses on how system architecture, user interface design, and communication mechanisms influence the feasibility of autonomous operation in rural and low-connectivity settings.    
Architectural analysis reveals that, despite the presence of edge computing components and multiple communication technologies, decision-making and fault recovery remain heavily dependent on human operators. The system therefore operates under a supervisory autonomy model, where the robot supports controlled behaviour but does not independently interpret sensor data or adapt to connectivity degradation. Evaluation of the user interface shows that technical data exposure, limited feedback, and reliance on user interpretation reduce usability for non-technical agricultural users. Communication analysis further demonstrates that multiple channels alone do not guarantee robustness unless they are integrated with adaptive system behaviour.   
The findings highlight that autonomy in rural agricultural robotics cannot be achieved through the addition of technological components alone. Instead, autonomy emerges from deliberate architectural allocation of responsibility, clear separation of control roles, and interface designs that support transparency and reduced cognitive load. This thesis contributes design-oriented insights for future rural robotic systems, emphasising contextual independence, supervisory interaction, architectural coherence, and simplicity as guiding principles for practical agricultural autonomy.

text: Software frameworks for rural AI robotics Robotic Autonomous robotic systems intended for agricultural environments must operate under conditions of unreliable connectivity, limited infrastructure, and high environmental variability. These constraints present significant challenges for system architecture, communication design, and human– robot interaction. This thesis investigates these challenges through the design, analysis, and evaluation of Nicobot, a mobile agricultural research platform developed to explore software frameworks for rural AI robotics.   
The research focuses on how system architecture, user interface design, and communication mechanisms influence the feasibility of autonomous operation in rural and low-connectivity settings.    
Architectural analysis reveals that, despite the presence of edge computing components and multiple communication technologies, decision-making and fault recovery remain heavily dependent on human operators. The system therefore operates under a supervisory autonomy model, where the robot supports controlled behaviour but does not independently interpret sensor data or adapt to connectivity degradation. Evaluation of the user interface shows that technical data exposure, limited feedback, and reliance on user interpretation reduce usability for non-technical agricultural users. Communication analysis further demonstrates that multiple channels alone do not guarantee robustness unless they are integrated with adaptive system behaviour.   
The findings highlight that autonomy in rural agricultural robotics cannot be achieved through the addition of technological components alone. Instead, autonomy emerges from deliberate architectural allocation of responsibility, clear separation of control roles, and interface designs that support transparency and reduced cognitive load. This thesis contributes design-oriented insights for future rural robotic systems, emphasising contextual independence, supervisory interaction, architectural coherence, and simplicity as guiding principles for practical agricultural autonomy.

year: 2026

title: “It is about enabling Tino Rangatiratanga and Mana Motuhake”: An analysis of submissions on the Pae Ora (Healthy Futures) Bill 2021 endorsing a Māori health authority

authors: Edmonds, Moengaroa

subjects: Health Equity

abstract: Indigenous leadership in healthcare is one way for Indigenous peoples to exercise sovereignty over their health. In Aotearoa New Zealand, the establishment of the Māori Health Authority (MHA) was grounded in a decades-long imperative to address Māori health inequities and operationalise te Tiriti o Waitangi within the health system. However, the populist National-led coalition government formed in November 2023 included the abolishment of the MHA in their first 100-day plan and eventually disestablished it in February 2024. This study analysed 155 public group submissions on the Pae Ora (Healthy Futures) Bill made in 2021 and representing health professionals, iwi, hapū, and community groups. Core themes endorsing the MHA as a statutory entity included honouring te Tiriti, advocating for Māori-led solutions to health inequities, decolonising health systems, and affirming Indigenous rights. The political decision to remove the MHA is antithetical to the explicit endorsement statements made by an overwhelming majority of group submitters with expertise in health organisational structures and healthcare provision. Our study has implications for future local and international research in documenting counter-narratives for Indigenous struggles in health systems.

text: “It is about enabling Tino Rangatiratanga and Mana Motuhake”: An analysis of submissions on the Pae Ora (Healthy Futures) Bill 2021 endorsing a Māori health authority Indigenous leadership in healthcare is one way for Indigenous peoples to exercise sovereignty over their health. In Aotearoa New Zealand, the establishment of the Māori Health Authority (MHA) was grounded in a decades-long imperative to address Māori health inequities and operationalise te Tiriti o Waitangi within the health system. However, the populist National-led coalition government formed in November 2023 included the abolishment of the MHA in their first 100-day plan and eventually disestablished it in February 2024. This study analysed 155 public group submissions on the Pae Ora (Healthy Futures) Bill made in 2021 and representing health professionals, iwi, hapū, and community groups. Core themes endorsing the MHA as a statutory entity included honouring te Tiriti, advocating for Māori-led solutions to health inequities, decolonising health systems, and affirming Indigenous rights. The political decision to remove the MHA is antithetical to the explicit endorsement statements made by an overwhelming majority of group submitters with expertise in health organisational structures and healthcare provision. Our study has implications for future local and international research in documenting counter-narratives for Indigenous struggles in health systems.

year: 2025