title: Some Ruthenium Derivatives of Penta-1,4-diyn-3-one

authors: Bruce, Michael I.

abstract: The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)₂CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]⁺ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([4][OTf]₂), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([5][OTf]₂). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knövenagel condensation of 2 with CH₂(CN)₂ affords {[Ru(dppe)Cp*]C≡C}₂C═C(CN) ₂ (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)₂]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the reaction between Ru{C≡CC(CN)═C(CN)₂}(dppe)Cp* and lithiated Ru(C≡CC≡CH)(dppe)Cp*. Single-crystal structural determinations of 2, [3]OTf, [5][OTf]₂, 6, 7, and 8 are reported, together with a supporting computational study of relevant electronic structures.

text: Some Ruthenium Derivatives of Penta-1,4-diyn-3-one The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)₂CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]⁺ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([4][OTf]₂), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]₂ ([5][OTf]₂). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knövenagel condensation of 2 with CH₂(CN)₂ affords {[Ru(dppe)Cp*]C≡C}₂C═C(CN) ₂ (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)₂]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the reaction between Ru{C≡CC(CN)═C(CN)₂}(dppe)Cp* and lithiated Ru(C≡CC≡CH)(dppe)Cp*. Single-crystal structural determinations of 2, [3]OTf, [5][OTf]₂, 6, 7, and 8 are reported, together with a supporting computational study of relevant electronic structures.

year: 2013

title: Two solutions for deflationism: assertion, explanation, and alethic desires

authors: Wyatt, Jeremy

abstract: Deflationists aim to upend traditional metaphysical inquiry about truth, proposing that we instead investigate why we think and speak about truth as we do. This iconoclastic agenda has faced a consistent barrage of criticisms, many of which have been ably dispatched. In this talk, I’ll focus on two recent challenges to deflationism about the concept TRUTH (or 'conceptual deflationism') that have yet to be addressed. Dorit Bar-On and Keith Simmons have argued that conceptual deflationists cannot account for the plausible Fregean idea that to assert a proposition is to present it as being true. In response, I’ll explain how revisiting the deflationary claim that facts involving TRUTH lack explanatory power reveals the compatibility of this Fregean proposal with conceptual deflationism. Even more recently, Jamin Asay has appealed to ‘alethic desires’ in arguing that TRUTH is a more robust concept than conceptual deflationists allow. The problem is meant to be that conceptual deflationists cannot accommodate the fact that someone who has a belief that p can desire that their belief be true without desiring that p. In response, I’ll explain why the case that Asay presents is likely a product of framing effects and thus poses no threat to conceptual deflationism.

text: Two solutions for deflationism: assertion, explanation, and alethic desires Deflationists aim to upend traditional metaphysical inquiry about truth, proposing that we instead investigate why we think and speak about truth as we do. This iconoclastic agenda has faced a consistent barrage of criticisms, many of which have been ably dispatched. In this talk, I’ll focus on two recent challenges to deflationism about the concept TRUTH (or 'conceptual deflationism') that have yet to be addressed. Dorit Bar-On and Keith Simmons have argued that conceptual deflationists cannot account for the plausible Fregean idea that to assert a proposition is to present it as being true. In response, I’ll explain how revisiting the deflationary claim that facts involving TRUTH lack explanatory power reveals the compatibility of this Fregean proposal with conceptual deflationism. Even more recently, Jamin Asay has appealed to ‘alethic desires’ in arguing that TRUTH is a more robust concept than conceptual deflationists allow. The problem is meant to be that conceptual deflationists cannot accommodate the fact that someone who has a belief that p can desire that their belief be true without desiring that p. In response, I’ll explain why the case that Asay presents is likely a product of framing effects and thus poses no threat to conceptual deflationism.

year: 2022

title: The Māori Data Privacy Framework: How useful is it for hapū?

authors: Clark, Vanessa

abstract: This brief is a part of a series, produced for the Tikanga in Technology (TiNT) research programme, that provides a hapū perspective on data sovereignty, data governance, and data privacy. In this brief we focus on the Māori Data Privacy Framework developed by the TiNT team and assess how useful it is for hapū. To do so, we draw on a case study with Ngāti Tiipa, one of the 33 iwi and hapū of the Waikato confederation (Kukutai, Whitehead & Kani, 2022). This brief should be read in conjunction with TiNT Brief #2 Protecting hapū data privacy: A Ngāti Tiipa case study of technology considerations.

text: The Māori Data Privacy Framework: How useful is it for hapū? This brief is a part of a series, produced for the Tikanga in Technology (TiNT) research programme, that provides a hapū perspective on data sovereignty, data governance, and data privacy. In this brief we focus on the Māori Data Privacy Framework developed by the TiNT team and assess how useful it is for hapū. To do so, we draw on a case study with Ngāti Tiipa, one of the 33 iwi and hapū of the Waikato confederation (Kukutai, Whitehead & Kani, 2022). This brief should be read in conjunction with TiNT Brief #2 Protecting hapū data privacy: A Ngāti Tiipa case study of technology considerations.

year: 2025-02-11