Optimising energy efficiency finance in emerging economies in Southeast Asia

University of Technology Sydney. Institute for Sustainable Futures.This thesis investigates the relationship between public and private sector efforts to optimise energy efficiency finance initiatives in an emerging country context, using Thailand as a case study. Demand-side energy efficiency measures could significantly reduce pressures on energy systems in emerging economies in Southeast Asia while at the same time reducing greenhouse gas emissions. Rapidly increasing energy needs, combined with dependence on fossil fuel imports have put energy systems in the region under pressure. Due to high urbanisation growth rates, and comparatively inefficient industries, demand-side energy efficiency measures could be part of the solution. The lack of external energy efficiency finance for industry and building owners is a major barrier, but reports and country examples contain mixed messages about how to best overcome this challenge. The dominant discourse around energy efficiency finance originates from international organisations who advocate for the public sector to focus all efforts on maximising private sector investments. However, developed country experience and some emerging country examples, suggest that the problem is more complex. Therefore, this thesis focuses on how to optimise energy efficiency finance. Thailand serves as a case study due to the range of energy efficiency initiatives designed and implemented in that country since the early 1990s. Transition studies and Multi-Level Perspective, were chosen as the theoretical framework and heuristic tool for the analysis. Qualitative data in the form of interviews with forty-eight experts from government, the private sector and academia form the core of this research. The research found that in Thailand, after more than 10 years of public sector support for energy efficiency finance initiatives, success in the private sector has been limited. Challenges identified include: (1) a lack of de-risking measures (2) renewable energy projects receiving most funding; (3) lack of guidance from the Central Bank of Thailand and (4) missing cross-coordination with relevant ministries to create additional demand for energy efficiency finance services. Suggestions for next steps are provided. The main finding from this research is that EEF in an emerging country context will never be transitioned 100% to the private sector, but will be reliant on long-term consistent support from the public sector. Policy makers and international organisations must therefore carefully evaluate the existing framework conditions before choosing which energy efficiency finance initiatives to support. The Multi-Level Perspective analytical framework could provide such an analytical tool to further unleash the energy efficiency potential in Southeast Asia

Modern NMR Spectroscopy for Exploring New Intermediates and Reaction Pathways in Organo- and Photocatalysis, Organometallic and Inorganic Chemistry

This thesis describes the investigation of new reaction pathways and intermediates in the fields of organo- and photocatalysis, organometallic and inorganic chemistry using modern NMR spectroscopy. Chapter 1 gives a general overview of the different topics. Chapter 2 describes the implementation of a broadband pulse in heteronuclear 1D and 2D NMR experiments for uniform and simultaneous excitation of a large frequency range of up to 500 or 1000 kHz. Chapter 3 presents mechanistic elucidations of an unusual formation of conjugated enynes with a junction to cyclic nitronates in the field of organocatalysis. Chapter 4 describes the first direct and photocatalytic functionalization of white phosphorus to important organic triaryl and tetraaryl phosphorus compounds. Chapter 5 reports the synthesis and characterization of a novel phospha-bora-norbornadiene which, due to its P-B bond, is a masked frustrated Lewis pair and has been shown to be reactive toward triple bonds of alkynes and nitriles. Chapter 6 addresses the synthesis and characterization of a novel iron complex that can either add or split CO2 depending on the coordination of its chelating ligand. Chapter 7 describes the isolation and investigation of two novel gold complexes, whereby NMR could provide insights into the reaction processes in liquid ammonia. Chapter 8 presents the detection and characterization of the first transition metal-functionalized and simultaneously protonated silicon-Zintl cluster in solution using NMR. Chapter 9 summarizes all the results of this work

On the Reactivity of NHCtBuAuCl towards Rb6Cs6Si17: The First Gold‐Silicon Cluster [(NHCtBuAu)6(η2‐Si4)]Cl2·7NH3 and an Imide Capped Gold Triangle (NHCtBuAu)3NHCl

Crystals of the two new compounds ((NHCAu)-Au-tBu)(3)NHCl and [((NHCAu)-Au-tBu)(6)(eta(2)-Si-4)]Cl-2 center dot 7NH(3)could be isolated from the reaction of Rb(6)Cs(6)Si(17)with (NHCAuCl)-Au-tBu in the presence of [2.2.2]-cryptand in liquid ammonia. Both compounds were characterized by single-crystal X-ray diffraction and crystallize trigonally without any alkali metals or chelating ligands. Additionally, the crystal of [((NHCAu)-Au-tBu)(6)(eta(2)-Si-4)]Cl-2 center dot 7NH(3)was further interpreted by means of ELF and NBO calculations. In the case of ((NHCAu)-Au-tBu)(3)NHCl, NMR experiments provided an exceptional insight into the reaction processes in solution and allowed for the detection of sequential precursors. In the class of capped gold triangles ((NHCAu)-Au-tBu)(3)NHCl impresses with its unique characteristics of being capped by an imide and bound toN-heterocyclic carbenes as ligands instead of the ubiquitously employed phosphines. The gold capped silicon tetrahedron [((NHCAu)-Au-tBu)(6)(eta(2)-Si-4)]Cl-2 center dot 7NH(3)represents the first known silicide-gold compound, as well as the first known functionalized Zintl anion, crystallized with a cationic central moiety

NMR‐Spectroscopic Detection of an Elusive Protonated and Coinage Metalated Silicide [NHC Dipp Cu(η 4 ‐Si 9 )H] 2− in Solution

A simultaneously protonated and functionalized silicide cluster [NHCDippCu(η4-Si9)H]2− was detected and characterized in liquid ammonia by NMR spectroscopy. Key NMR results were corroborated by theoretical calculations. 1H-NMR line-widths at variable temperatures revealed that proton hopping in the metalated complex [NHCDippCu(η4-Si9)H]2− is less pronounced than in the non-complexed silicide [HSi9]3−. Besides [HSi9]3− and [NHCDippCu(η4-Si9)H]2− also the unprotonated analogous cluster [NHCDippCu(η4-Si9)]3− was detected in solution. In addition, a new 29Si-NMR signal was obtained in the course of 29Si-NMR studies that we assigned to [NHCDippCu(η4-Si9)]3−. The isolation of crystals of (K[2.2.2]-crypt)2K0.48Rb3.52[NHCDippCu(η4-Si9)]2 prove the availability of the non-protonated NHCDippCu(η4-Si9) fragment in solution. To the best of our knowledge the detection of [NHCDippCu(η4-Si9)H]2− represents the first case of a protonated and coinage metalated group 14 Zintl cluster in solution so far

Facile C=O Bond Splitting of Carbon Dioxide Induced by Metal-Ligand Cooperativity in a Phosphinine Iron(0) Complex

New iron complexes [Cp*FeL](-) (1-sigma and 1-pi, Cp*=C5Me5) containing the chelating phosphinine ligand 2-(2 '-pyridyl)-4,6-diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO2 with the isomer 1-pi, in which L binds to Fe through the phosphinine moiety in an eta(5) fashion, leads to the formation of 3-pi, in which CO2 has undergone electrophilic addition to the phosphinine group. In contrast, interaction with 1-sigma-in which L acts as a sigma-chelating [P,N] ligand-leads to product 3-sigma in which one C=O bond has been completely broken. Such CO2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre

Transition-Metal-Stabilized Heavy Tetraphospholide Anions

Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP42– and PbP42–. The complexes [(η4-tBu2C2P2)2Co2(μ,η5:η5–P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar′TtCo(η4-P2C2tBu2)(η4–COD)] [Tt = Sn (2), Pb (3), Ar′ = C6H3-2,6{C6H3-2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(η4-P2C2tBu2)(COD)}2 [Tt = Sn (4), Pb (5)]. While the SnP42– complex 6 was isolated as a pure and stable compound, compound 7 eliminated Pb(0) below room temperature to afford [(η4-tBu2C2P2)2Co2(μ,η4:η4–P4) (8), which is a rare example of a tripledecker complex with a P42– middle deck. The electronic structures of 6–8 are analyzed using theoretical methods including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby, the aromatic nature of P5– and SnP42– was confirmed, while for P42–, a specific type of symmetry-induced weak paramagnetism was found that is distinct from conventional antiaromatic species

Implementation of nationally determined contributions : Indonesia country report

The study analyses the country background, emissions trends, ongoing activities and barriers relating to the implementation of the Nationally Determined Contribution (NDC) of Indonesia under the UNFCCC. A special emphasis is laid on further mitigation potentials. Fields of mitigation assessed are land use, land use change and forestry (LULUCF) governance and monitoring as well as electricity demand and generation. A chapter is dedicated to the ongoing and planned increase in coal use - contrary to mitigation ambition in other fields - including an analysis of the economic role and local impacts of coal

Transition-Metal-Stabilised Heavy Tetraphospholide Anions

Phosphorus analogues of the ubiquitous cyclopentadienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heaviear group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopen-tadienyl anions (SnP4)2─ and (PbP4)2─. The complexes [(η4-tBu2C2P2)2Co2(μ,η5:η5-P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar′TtCo(η4-P2C2tBu2)(η4-COD)] [Sn (2), Pb (3), Ar′ = C6H3-2,6{C6H3¬-2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(η4-P2C2tBu2)(COD)}2 [Tt = Sn (4), Pb (5)]. While the (SnP4)2− complex 6 was isolated as a pure and stable compound, compound 7 eliminates Pb(0) below room temper-ature to afford [(η4-tBu2C2P2)2Co2(μ,η4:η4-P4) (8), which is a rare example of a tripledecker complex with a (P4)2─ middle deck. The electronic structures of 6-8 are analysed using theoretical methods, including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby the aromatic nature of (P5)− and (SnP4)2− was confirmed, while for (P4)2− a specific type of symmetry-induced weak paramagnetism was found which is distinct from conventional antiaromatic species

Photochemical transformation of chlorobenzenes and white phosphorus into arylphosphines and phosphonium salts

Chlorobenzenes are important starting materials for the preparation of commercially valuable triarylphosphines and tetraarylphosphonium salts, but their use for the direct arylation of elemental phosphorus has been elusive. Here we describe a simple photochemical route toward such products. UV-LED irradiation (365 nm) of chlorobenzenes, white phosphorus (P4) and the organic superphotoreductant tetrakis(dimethylamino)ethylene (TDAE) affords the desired arylphosphorus compounds in a single reaction step