title: Preparation of buta-1,3-diynyl complexes of platinum(II) and their use in the construction of neutral molecular squares: synthesis, structural and theoretical characterisation of cyclo-{Pt(µ-C≡CC≡C)(dppe)}₄ and related chemistry

authors: Bruce, Michael I.

subjects: Chemistry

abstract: Copper(I)-catalysed reactions of cis-PtCl₂(L)₂ (L = Pet₃, L₂= dppe, dppp) with buta-1,3-diyne have given the corresponding diynyl complexes, cis-Pt(C≡CC≡CH)2(L)2 (L = Pet₃ 1, L₂= dppe 2, dppp 3) whose solid-state structures have been determined from single crystal X-ray diffraction studies. Theoretical calculations were carried out to probe the electronic structure of these diynyl complexes. Complex 2 reacts with Co₂(CO)₈ to give a bis-adduct 5 and with Ru₃(µ-dppm)(CO)₁₀ to give a mono-adduct 6; in both, the least hindered C≡C triple bond(s) is(are) coordinated. Lithiation (LiBut) of 2 gives a dilithio derivative, which has been converted to dimethyl 7 or mono-SiMe₃ 8 or -Au(PPh₃) 9 complexes. Cu(I) and Ag(I) (MI) adducts ( tweezer  complexes) have been obtained from reactions of 2 with MISCN or [MI(NCMe)₄]⁺. An ES mass spectrometric study of the interactions of 2 with Group 1 cations and with Tl⁺ is also described; comparative experiments with {W(CO)₃Cp}₂(µ-C₈), in which the four C≡C triple bonds do not have a  tweezer  conformation, have also been carried out. The degree of association is determined by the competitive solvation of the Group 1 cation. Coupling of the buta-1,3-diynyl complexes with Pt(OTf)₂(L )₂ gives homo- or mixed-ligand molecular squares cyclo-{(L)₂Pt(µ-C CC C)₂Pt(L )₂}₂ (L, L = Pet₃, L₂, L ₂= dppe, dppp; not all combinations), of which the molecular structure of cyclo-{Pt(µ-C CC C)(dppe)}₄ 17 is described (as solvates containing dmso). The molecular squares form adducts with substituted ammonium triflates [NH₂R₂][OTf] (R = Et, Pri, Cy; NH₂R₂= dbuH) and with Group 11 cations [MI(NCMe)]⁺.

text: Preparation of buta-1,3-diynyl complexes of platinum(II) and their use in the construction of neutral molecular squares: synthesis, structural and theoretical characterisation of cyclo-{Pt(µ-C≡CC≡C)(dppe)}₄ and related chemistry Copper(I)-catalysed reactions of cis-PtCl₂(L)₂ (L = Pet₃, L₂= dppe, dppp) with buta-1,3-diyne have given the corresponding diynyl complexes, cis-Pt(C≡CC≡CH)2(L)2 (L = Pet₃ 1, L₂= dppe 2, dppp 3) whose solid-state structures have been determined from single crystal X-ray diffraction studies. Theoretical calculations were carried out to probe the electronic structure of these diynyl complexes. Complex 2 reacts with Co₂(CO)₈ to give a bis-adduct 5 and with Ru₃(µ-dppm)(CO)₁₀ to give a mono-adduct 6; in both, the least hindered C≡C triple bond(s) is(are) coordinated. Lithiation (LiBut) of 2 gives a dilithio derivative, which has been converted to dimethyl 7 or mono-SiMe₃ 8 or -Au(PPh₃) 9 complexes. Cu(I) and Ag(I) (MI) adducts ( tweezer  complexes) have been obtained from reactions of 2 with MISCN or [MI(NCMe)₄]⁺. An ES mass spectrometric study of the interactions of 2 with Group 1 cations and with Tl⁺ is also described; comparative experiments with {W(CO)₃Cp}₂(µ-C₈), in which the four C≡C triple bonds do not have a  tweezer  conformation, have also been carried out. The degree of association is determined by the competitive solvation of the Group 1 cation. Coupling of the buta-1,3-diynyl complexes with Pt(OTf)₂(L )₂ gives homo- or mixed-ligand molecular squares cyclo-{(L)₂Pt(µ-C CC C)₂Pt(L )₂}₂ (L, L = Pet₃, L₂, L ₂= dppe, dppp; not all combinations), of which the molecular structure of cyclo-{Pt(µ-C CC C)(dppe)}₄ 17 is described (as solvates containing dmso). The molecular squares form adducts with substituted ammonium triflates [NH₂R₂][OTf] (R = Et, Pri, Cy; NH₂R₂= dbuH) and with Group 11 cations [MI(NCMe)]⁺.

year: 2002-01-01

title: Roofing that generates electricity and heat

authors: Bura, Sunil Kumar

subjects: roofing

abstract: Integrating solar energy devices with building products is a rapidly growing market in the building industry. The aim is to make solar devices that integrate into a standard facade, window, roof tile, membrane roof or long run roof. These serve as weatherproofing for a building and also generate electrical and thermal energy.

text: Roofing that generates electricity and heat Integrating solar energy devices with building products is a rapidly growing market in the building industry. The aim is to make solar devices that integrate into a standard facade, window, roof tile, membrane roof or long run roof. These serve as weatherproofing for a building and also generate electrical and thermal energy.

year: 2008

title: Supervision as cultural partnership: Contributions to dialogue

authors: Crocket, Kathie

abstract: The term cultural supervision has been coined as part of a strategy that implicates supervision in the support and development of culturally appropriate therapeutic practice. In Aotearoa New Zealand particular focus has been given to supervision where the client is Māori and the practitioner is a member of the dominant Pākehā culture particularly, or of other non-Māori cultures. However, while the phrase cultural supervision has entered common professional parlance, the practice has had little research attention in counselling/psychotherapy in New Zealand. Cultural supervision appears to encompass a range of understandings, and there is no clear agreement about practice implications. It is unclear what alignment there is between aspirations, regulations, and practice. This article reports on an exploratory qualitative study that investigated how supervision might work in supporting culturally appropriate counselling practice in Aotearoa New Zealand. The study’s findings are presented as a multi-voiced dialogue. This arts-based representational practice enacts the uncertainties of post-colonial experience. Its intention is to make assumptions, ideas, and practices available for discussion. Its contribution is to join current dialogue about supervision and culture, and to raise further questions about how supervision and culturally appropriate practice come together.

text: Supervision as cultural partnership: Contributions to dialogue The term cultural supervision has been coined as part of a strategy that implicates supervision in the support and development of culturally appropriate therapeutic practice. In Aotearoa New Zealand particular focus has been given to supervision where the client is Māori and the practitioner is a member of the dominant Pākehā culture particularly, or of other non-Māori cultures. However, while the phrase cultural supervision has entered common professional parlance, the practice has had little research attention in counselling/psychotherapy in New Zealand. Cultural supervision appears to encompass a range of understandings, and there is no clear agreement about practice implications. It is unclear what alignment there is between aspirations, regulations, and practice. This article reports on an exploratory qualitative study that investigated how supervision might work in supporting culturally appropriate counselling practice in Aotearoa New Zealand. The study’s findings are presented as a multi-voiced dialogue. This arts-based representational practice enacts the uncertainties of post-colonial experience. Its intention is to make assumptions, ideas, and practices available for discussion. Its contribution is to join current dialogue about supervision and culture, and to raise further questions about how supervision and culturally appropriate practice come together.

year: 2015