Remote functionalisation via sodium alkylamidozincate intermediates : access to unusual fluorenone and pyridyl ketone reactivity patterns

Treating fluorenone or 2-benzoylpyridine with the sodium zincate [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] in hexane solution, gives efficient Bu-t addition across the respective organic substrate in a highly unusual 1,6-fashion, producing isolable organometallic intermediates which can be quenched and aerobically oxidised to give 3-tert-butyl-9H-fluoren-9-one and 2-benzoyl-5-tert-butylpyridine respectively

Live Fast, Die Young: GMC lifetimes in the FIRE cosmological simulations of Milky Way-mass galaxies

We present the first measurement of the lifetimes of giant molecular clouds (GMCs) in cosmological simulations at z = 0, using the Latte suite of FIRE-2 simulations of Milky Way (MW) mass galaxies. We track GMCs with total gas mass ≳10⁵ M⊙ at high spatial (∼1 pc), mass (7100 M⊙), and temporal (1 Myr) resolution. Our simulated GMCs are consistent with the distribution of masses for massive GMCs in the MW and nearby galaxies. We find GMC lifetimes of 5–7 Myr, or 1–2 freefall times, on average, with less than 2 per cent of clouds living longer than 20 Myr. We find decreasing GMC lifetimes with increasing virial parameter, and weakly increasing GMC lifetimes with galactocentric radius, implying that environment affects the evolutionary cycle of GMCs. However, our GMC lifetimes show no systematic dependence on GMC mass or amount of star formation. These results are broadly consistent with inferences from the literature and provide an initial investigation into ultimately understanding the physical processes that govern GMC lifetimes in a cosmological setting

An assessment of high touch object cleaning thoroughness using a fluorescent marker in two Australian hospitals

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Lithium dihydropyridine dehydrogenation catalysis : a group 1 approach to cyclisation of diamine-boranes

In reactions restricted previously to a ruthenium catalyst, a 1-lithium-2-alkyl-1,2-dihydropyridine complex is shown to be a competitive alternative dehydrogenation catalyst for the transformation of diamine boranes to cyclic 1,3,2-diazaborolidines, which can in turn be smoothly arylated in good yields. This study establishes the conditions and solvent dependence of the catalysis via NMR monitoring, with mechanistic insight provided by NMR (including DOSY) experiments and X-ray crystallographic studies of several model lithio intermediates

Accessible heavier s-block dihydropyridines : structural elucidation and reactivity of isolable molecular hydride sources

The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone

Live Fast, Die Young: GMC lifetimes in the FIRE cosmological simulations of Milky Way-mass galaxies

We present the first measurement of the lifetimes of giant molecular clouds (GMCs) in cosmological simulations at z = 0, using the Latte suite of FIRE-2 simulations of Milky Way (MW) mass galaxies. We track GMCs with total gas mass ≳10⁵ M⊙ at high spatial (∼1 pc), mass (7100 M⊙), and temporal (1 Myr) resolution. Our simulated GMCs are consistent with the distribution of masses for massive GMCs in the MW and nearby galaxies. We find GMC lifetimes of 5–7 Myr, or 1–2 freefall times, on average, with less than 2 per cent of clouds living longer than 20 Myr. We find decreasing GMC lifetimes with increasing virial parameter, and weakly increasing GMC lifetimes with galactocentric radius, implying that environment affects the evolutionary cycle of GMCs. However, our GMC lifetimes show no systematic dependence on GMC mass or amount of star formation. These results are broadly consistent with inferences from the literature and provide an initial investigation into ultimately understanding the physical processes that govern GMC lifetimes in a cosmological setting

1-Alkali-metal-2-alkyl-1,2-dihydropyridines : soluble hydride surrogates for catalytic dehydrogenative coupling and hydroboration applications

Equipped with excellent hydrocarbon solubility, the lithium hydride surrogate 1-lithium-2-t-butyl-1,2-dihydropyridine (1tLi) functions as a precatalyst to convert Me2NH·BH3 to [NMe2BH2]2 (89% conversion) under competitive conditions (2.5 mol%, 60h, 80°C, toluene solvent) to that of previously reported LiN(SiMe3)2. Sodium and potassium dihydropyridine congeners produce similar high yields of [NMe2BH2]2 but require longer times. Switching the solvent to pyridine induces a remarkable change in the dehydrocoupling product ratio, with (NMe2)2BH favoured over [NMe2BH2]2 (e.g., 94%:2% for 1tLi). Demonstrating its versatility, precatalyst 1tLi was also successful in promoting hydroboration reactions between pinacolborane and a selection of aldehydes and ketones. Most reactions gave near quantitative conversion to the hydroborated products in 15 minutes, though sterically demanding carbonyl substrates require longer times. The mechanisms of these rare examples of group 1 metal catalysed processes are discussed

Lithium diamidodihydridoaluminates : bimetallic cooperativity in catalytic hydroboration and metallation applications

Cooperativity between the Li and Al centres is implicated in catalytic hydroboration reactions of aldehydes and ketones with pinacolborane via heteroleptic lithium diamidodihydridoaluminates. In addition to implementing hydroalumination, these versatile heteroleptic ates can also perform as amido bases as illustrated with an acidic triazole

A regioselectively 1, 1',3 ,3'-tetrazincated ferrocene complex displaying core and peripheral reactivity

Regioselective 1,1′,3,3′-tetrazincation [C-H to C-Zn(tBu)] of ferrocene has been achieved by reaction of a fourfold excess of di-t-butylzinc (tBu2Zn) with sodium 2,2,6,6-tetramethylpiperidide (NaTMP) in hexane solution manifested in the trimetallic iron-sodium-zinc complex [Na4(TMP)4Zn4(tBu)4{(C5H3)2Fe}], 1. X-ray crystallographic studies supported by DFT modelling reveal the structure to be an open inverse crown in which two [Na(TMP)Zn(tBu)Na(TMP)Zn(tBu)]2+ cationic units surround a {(C5H3)2Fe}4- tetraanion. Detailed C6D6 NMR studies have assigned the plethora of 1H and 13C chemical shifts of this complex. It exists in a major form in which capping and bridging TMP groups interchange, as well as a minor form that appears to be an intermediate in this complicated exchange phenomenon. Investigation of 1 has uncovered two distinct reactivities. Two of its peripheral t-butyl carbanions formally deprotonate toluene at the lateral methyl group to generate benzyl ligands that replace these carbanions in [Na4(TMP)4Zn4(tBu)2(CH2Ph)2{(C5H3)2Fe}], 2, which retains its tetrazincated ferrocenyl core. Benzyl-Na π-arene interactions are a notable feature of 2. In contrast, reaction with pyridine affords the crystalline product {[Na·4py][Zn(py∗)2(tBu)·py]}∞, 3, where py is neutral pyridine (C5H5N) and py∗ is the anion (4-C5H4N), a rare example of pyridine deprotonated/metallated at the 4-position. This ferrocene-free complex appears to be a product of core reactivity in that the core-positioned ferrocenyl anions of 1, in company with TMP anions, have formally deprotonated the heterocycle