Orthomercurated and cycloaurated derivatives of the iminophosphorane Ph3P NPh

Ortho-lithiation of Ph3P NPh followed by reaction with HgCl2 gave good yields of [Hg{C6H4(PPh2 NPh)-2}Cl], 3, which was characterised spectroscopically and by an X-ray crystal structure determination. This is an isomer of the product of direct mercuration of Ph3P NPh which occurs on the N-bonded phenyl ring [J. Vicente, J.A. Abad, R. Clemente, J. Lopez-Serrano, M.C. Ramirez de Arellano, P.G. Jones, D. Bautista, Organometallics, 22 (2003) 4248]. Transmetallation of 3 with [AuCl4]− gave the corresponding cycloaurated complex [Au{κ2-C,N-C6H4(PPh2 NPh)-2}Cl2], with a five-membered metallocyclic ring incorporating four different elements

Transgressive technologies? Strategies of discursive containment in the representation and regulation of assisted reproductive technologies in Aotearoa/New Zealand

Drawing on a case study of the contemporary representation and regulation of assisted reproductive technologies (ARTs) in Aotearoa/New Zealand, this article traces the cultural anxieties evident in public, political, and media discussion and debate around the provision and use of ART, with a specific focus on the use of donor insemination and IVF by single women and lesbian couples. It documents the operation of various narrative mechanisms, normative assumptions, and discursive strategies that work to identify the legitimate uses and users of such technologies whilst simultaneously affirming conventional understandings of "gender", "motherhood", and "the family", and concludes that contemporary anxieties and ethical dilemmas provoked by women's transgressive uses of ART have been addressed through legislative changes that target certain groups of women for official surveillance and control while also effectively limiting their reproductive options

Kinds of conversational cooperation

The Cooperative Principle was the organizing principle in Grice’s pragmatics. More recently, cooperation has played a reduced role in pragmatic theory. The principle has been attacked on the grounds that people are not always or generally cooperative. One response to that objection is to say that there are two kinds of cooperation and Grice’s principle only applies to the narrower kind, which concerns linguistic or formal cooperation. I argue that such a distinction is only defensible if it is accepted that linguistic cooperation can be determined by an extra-linguistic goal. To make distinctions among types of cooperation is helpful but this strategy does not remove all concerns about speakers who are not fully cooperative and in particular the operation of the principle needs to be qualified in situations of conflict of interest. I propose that the principle, once qualified, can have a significant continuing role in pragmatic theory

Synthesis and alkyne-coupling chemistry of cyclomanganated 1- and 3-acetylindoles, 3-formylindole and analogues

The syntheses are reported of new cyclomanganated indole derivatives (1-acetyl-κO-indolyl-κC2)dicarbonylbis(trimethylphosphite)manganese (2), (1-methyl-3-acetyl-κO-indolyl-κC2)tetracarbonylmanganese (4), (3-formyl-κO-indolyl-κC2)tetracarbonylmanganese (5a) and (1-methyl-3-formyl-κO-indolyl-κC2)tetracarbonylmanganese (5b). The unusually complicated crystal structure of 5b has been determined, the first for a cyclomanganated aryl aldehyde. The preparations of a mitomycin-related pyrrolo-indole and related products by thermally promoted and oxidatively (Me3NO) initiated alkyne-coupling reactions of the previously known complex (1-acetyl-κO-indolyl-κC2)tetracarbonylmanganese (1) are reported for different alkynes and solvents. X-ray crystal structures are reported for the dimethyl acetylenedicarboxylate coupling product of 1 (dimethyl 1-methyl-l-hydroxypyrrolo[1,2a]-indole-2,3-dicarboxylate; 6a), and an unusually-cyclised triple insertion product 8 from the coupling of acetylene with 4, in which a cyclopentadiene moiety is η3-allyl-coordinated to Mn through only one double bond and an exocyclic carbon, but which rearranges on heating to an η5-cyclopentadienyl complex

Anomalous reaction of an aryl silane with Co₂ (CO)₂; characterisation of Me ₂NC₆H₄Si[Co(CO)₄][OCCo₃(CO)₉]₂

Reaction of Me₂NC₆H₄SiH₃ with Co₂(CO)₈ gave Me₂NC₆H₄Si[Co(CO)₄][OCCo₃(CO)₉]₂ which was shown to have one –Co(CO)₄ group and two –OCCo₃(CO)₉ cluster units bonded to the silicon atom

Manganese carbonyl-mediated reactions of azabutadienes with phenylacetylene, methyl acrylate and other unsaturated molecules

Reaction of PhCH₂Mn(CO)₅ with l,4-di-aryl-1-aza-1,3-butadienes gave substituted pyrrolinonyl rings which were η⁴-coordinated to a Mn(CO)₃ group. These are formed by intramolecular CO insertion into a (non-isolated) cyclomanganated intermediate, followed by cyclisation. Other unsaturated reagents (PhC≡CH, CH2=CHCOOMe, PhNCO) gave products arising from insertion of these, including a structurally characterised tri-aryl-η⁵-azacyclohexadienyl-Mn(CO)₃ complex from the reaction with the alkyne. PhCH₂Mn(CO)₅ reacts with l,4-di-aryl-1-aza-1,3-butadienes in the presence of unsaturated substrates to give products based on a cyclomanganated intermediate

Six-coordinate organotin(IV) complexes formed using the Kläui ligands; [CpCo{P(OR′)2O}3]SnR3 − nCln

The complexes [CpCo{P(OR′)2O}3]SnR3 − nCln [R′ = Me, Et; R = Ph, Me] are readily prepared from the corresponding organotin chloride and the sodium salt of the Kläui ligands. The X-ray crystal structures of the full series are reported for R = Ph, n = 0-3, and these show that they are all six-coordinate, including the Ph3Sn derivative which is the first example of a SnC3O3 coordination sphere. 1H, 13C, 31P and 119Sn NMR spectra are reported, and interpreted in terms of significant second-order effects and fluxional processes

A structural, spectroscopic and theoretical study of the triphenylphosphine chalcogenide complexes of tungsten carbonyl, [W(XPPh3)(CO)5], X=O, S, Se

The series [W(XPPh3)(CO)5], X=O, S, Se has been structurally determined by X-ray crystallography and fully characterised spectroscopically to provide data for comparing the bonding of the Ph3PX ligands to the metal. The P-X-W angles are 134.3°, 113.2° and 109.2°, respectively, for X=O, S, Se. The bonding has been analysed using EHMO calculations which suggest that lower P-X-W angles depend on the relative importance of σ-bonding, which in turn depends on the chalcogen in the order X=Se > S > O. The effect is enhanced by lower energies of the metal σ and π orbital energies

New complexes with M-Si-O or M-Si-S linkages (M = Fe or Co)

Ph2XSiFe(CO)2Cp [X = p-tolylS (1a), MeO (1b)] and Ph[2-MeOC6H4]XSiFe(CO)2Cp [X = Cl (2a), OMe (2b)] have been fully characterised, including X-ray crystal structure determinations for 1a, 1b and 2a. None of the examples showed any tendency for migration of the X groups from silicon to iron, with elimination of silylene. However very ready loss of the X groups was seen in the electrospray mass spectra, suggesting formation of the cationic silylene-iron complex ions is favoured. This was especially so for 2a and 2b, where intramolecular stabilisation of the silicon centre from the 2-OMe group is possible.The stable siloxane O[SiPh2{Co(CO)4}]2 was also characterised; the X-ray crystal structure analysis shows a Si-O-Si bond angle of 153°

Efficient routes to epimerically-pure side-chain derivatives of lanosterol

A technically simple route is described to individual epimers of side-chain derivatives of lanosterol (3-hydroxy-5-lanosta-8,24-diene). Epimerically pure 24,25-epoxy-, 24,25-dihydroxy- and 24-bromo-25-hydroxy-lanosterol have been prepared in good yield from commercial (50-60%) lanosterol. Hypophosphorous acid was used as a catalyst for the cohalogenation of the 24(25) bond and also for the efficient conversion of 24,25-epoxy- and 24-bromo-25-hydroxylanosterol to epimerically pure 24(R) or 24(S)-24,25-dihydroxylanosterols