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Group 3- and 4f-element organometallic chemistry and reactivity are decisively driven by the rare-earth-metal/lanthanide (Ln) ion size and associated electronegativity/ionicity/Lewis acidity criteria. For these reasons, the synthesis of terminal "unsupported" imides [Ln═NR] of the smaller, closed-shell Sc(III), Lu(III), Y(III), and increasingly covalent Ce(IV) has involved distinct reaction protocols while derivatives of the "early" large Ln(III) have remained elusive. Herein, we report such terminal imides of open-shell lanthanide cations Ce(III), Nd(III), and Sm(III) according to a new reaction protocol. Lewis-acid-stabilized methylidene complexes [Tp

Elucidation of the role of infectious agents putatively involved in gill disease is commonly hampered by the lack of culture systems for these organisms. In this study, a farmed population of Atlantic salmon pre-smolts, displaying proliferative gill disease with associated Candidatus Branchiomonas cysticola, Ca. Piscichlamydia salmonis and Atlantic salmon gill pox virus (SGPV) infections, was identified. A subpopulation of the diseased fish was used as a source of waterborne infection towards a population of naive Atlantic salmon pre-smolts. Ca. B. cysticola infection became established in exposed naive fish at high prevalence within the first month of exposure and the bacterial load increased over the study period. Ca. P. salmonis and SGPV infections were identified only at low prevalence in exposed fish during the trial. Although clinically healthy, at termination of the trial the exposed, naive fish displayed histologically visible pathological changes typified by epithelial hyperplasia and subepithelial inflammation with associated bacterial inclusions, confirmed by fluorescent in situ hybridization to contain Ca. B. cysticola. The results strongly suggest that Ca. B. cysticola infections transmit directly from fish to fish and that the bacterium is directly associated with the pathological changes observed in the exposed, previously naive fish.

A series of 3,5-substituted tris(pyrazolyl)borate (TpR,Me; R = Me, Ph, tBu) complexes of the alkaline-earth metals (Mg, Ca, Ba) was synthesized by salt metathesis reactions. The influence of different organometallic precursors on Schlenk-type rearrangement reactions was studied, putting emphasis on the metal size and the steric encumbrance of the Tp ligands. Magnesium alkyls MgR2 (R = AlMe4, CH3) react with KTpR,Me to form the heteroleptic complexes (TpMe,Me)Mg(CH3), (TptBu,Me)Mg(CH3), and (TpMe,Me)Mg(AlMe4). The latter tetramethylaluminate complex can also be obtained by treatment of TpMe,MeMg(CH3) with an excess of trimethylaluminum. The formally six-coordinate cyclopentadienyl derivative (C5Me5)Mg(Me)(thf)2 is synthesized from MeMgBr and 1 equiv of K(C5Me5). Equimolar reactions of the tetraethylaluminates [M(AlEt4)2]n of the heavier alkaline-earth metals calcium and barium with KTpR,Me give the homoleptic complexes of Ca(TpR,Ph)2 and Ba(TpR,Me)2. Heterotrimetallic [BaK(AlEt4)3]n is identified as a liga...

As an approach to combat bacterial infections, incorporation of florfenicol in Atlantic cod ( Gadus morhua ) larvae, administered orally through bioencapsulation in Artemia franciscana nauplii, was investigated. Artemia nauplii were enriched with 1000 mg/l florfenicol for 30 min and administered as a single dose, or daily for three consecutive days. The concentration of florfenicol in the medicated nauplii, and in the cod larvae, was analysed by high performance liquid chromatography (HPLC). Following a single oral administration, the elimination half-life ( t ½ β) was calculated to 14 h, C max to 4.7 μg/g dry weight (14.3 ng/larva), T max to 0.5 h, and MRT to 20 h, respectively. An hour after administration of batch 1 in the triple dose study, a mean florfenicol concentration of 4.6 μg/g dry weight (14.0 ng/larva) was found in the cod larvae. One hour following administration of batch 2 and 3, corresponding values were 5.9 μg/g dry weight (17.9 ng/larva) and 4.2 μg/g dry weight (12.8 ng/larva), respectively. These data show that medication of cod larvae using Artemia nauplii as carriers of florfenicol is a promising approach for treatment.

Quinolyl-substituted half-sandwich complexes (CpQ)Ln(AlMe4)2 (CpQ = 2,3,4,5-tetramethyl-1-(8-quinolyl)cyclopentadienyl; Ln = Y, La) were obtained in quantitative yield via protonolysis reactions utilizing HCpQ and homoleptic tetramethylaluminates Ln(AlMe4)3. X-ray structure analyses revealed that the quinolyl-substituted cyclopentadienyl ligand coordinates to the rare-earth metal centers in an η5:η1 fashion through the Cp ring carbon atoms and the N atom of the quinolyl substituent. The complexes (CpQ)Ln(AlMe4)2 show good activity and high trans-1,4-stereoselectivity (maximum 93%) in the polymerization of isoprene upon activation with the organoborates [Ph3C][B(C6F5)4] and [PhNMe2H][B(C6F5)4]. The effects of metal size, cocatalyst, temperature, and solvent were assessed in these polymerization reactions, and the performance of such N-donor-functionalized complexes was compared to that of (CpR)Ln(AlMe4)2 containing different types of nondonor-functionalized cyclopentadienyl ligands.

Homoleptic tetramethylgallate Lu(GaMe4)3 reacts selectively with superbulky (TptBu,Me)H according to a methane elimination reaction, affording the quantitative formation of monomeric base-free low-coordinate (TptBu,Me)LuMe2. Weak interaction of the strongly basic lanthanide methyl groups with the comparatively weak Lewis acid trimethylgallium in Lu(GaMe4)3 is indicated by their separation into [LuMe3]n and GaMe3 even at −35 °C.

Mononuclear heterobimetallic complexes (TptBu,Me)Yb(AlR4) (R = Me, Et) were obtained in high yields according to a silylamide elimination protocol employing (TptBu,Me)Yb[N(SiMe3)2] and AlR3. The solid-state structures revealed κ3-coordinated TptBu,Me ligands and η2-coordinated [AlR4] moieties, with additional Yb···H agostic interactions from the bridging methyl and methylene groups of the [AlR4] ligands. These agostic interactions however are not strong enough to maintain a rigid structure in solution. 1H NMR spectroscopy showed a highly fluxional ligand environment with only one set of signals for both TptBu,Me and [AlR4] ligands at temperatures down to −80 °C.

The first cases of heart and skeletal muscle inflammation (HSMI), in Atlantic salmon Salmo salar were registered in 1999 in the Hitra/Frøya area of Norway. The disease has since spread south to Rogaland, i.e. the southernmost county with salmon farming in Norway. The disease outbreaks usually start 5 to 9 mo after release into seawater but may occur as early as 2 wk after sea release. The present study focuses on possible pathogens associated with HSMI. It was not possible to find any parasites or bacteria that could explain HSMI, and none of the well-known viruses (infectious salmon anaemia virus, Norwegian salmonid alphavirus, infectious pancreatic necrosis virus, Atlantic salmonid paramyxovirus) were consistently present. Use of transmission electron microscopy showed the presence of epitheliocystis agent in 3 of 4 farms included in this study, and several virus-like particles. Type I and Type II virus particles, previously described for salmon suffering from haemorrhagic smolt syndrome (HSS), and erythrocytic inclusion body syndrome (EIBS) virus were consistently present in salmon suffering from HSMI in all 4 farms included in this study. The 2 HSS viruses (Type I and Type II) were also cultured in Atlantic salmon kidney (ASK) cells from salmon suffering from HSMI. However, a causal relationship between the observed virus particles and HSMI remains to be demonstrated.

Whereas a number of homoleptic metal(III) tetramethylaluminates M(AlMe(4))(3) of the rare earth metals have proven accessible, the stability of these compounds varies strongly among the metals, with some even escaping preparation altogether. The differences in stability may seem puzzling given that this class of metals usually is considered to be relatively uniform with respect to properties. On the basis of quantum chemically obtained relative energies and atomic and molecular descriptors of homoleptic tris(tetramethylaluminate) and related compounds of rare earth metals, transition metals, p-block metals, and actinides, multivariate modeling has identified the importance of ionic metal-methylaluminate bonding and small steric repulsion between the methylaluminate ligands for obtaining stable homoleptic compounds. Low electronegativity and a sufficiently large ionic radius are thus essential properties for the central metal atom. Whereas scandium and many transition metals are too small and too electronegative for this task, all lanthanides and actinides covered in this study are predicted to give homoleptic compounds stable toward loss of trimethylaluminum, the expected main decomposition reaction. Three of the predicted lanthanide-based compounds Ln(AlMe(4))(3) (Ln = Ce, Tm, Yb) have been prepared and fully characterized in the present work, in addition to Ln(OCH(2)tBu)(3)(AlMe(3))(3) (Ln = Sc, Nd) and [Eu(AlEt(4))(2)](n). At ambient temperature, donor-free hexane solutions of Ln(AlMe(4))(3) of the Ln(3+)/Ln(2+) redox-active metal centers display enhanced reduction to [Ln(AlMe(4))(2)](n) with decreasing negative redox potential, in the order Eu ≫ Yb ≫ Sm. Whereas Eu(AlMe(4))(3) could not be identified, Yb(AlMe(4))(3) turned out to be isolable in low yield. All attempts to prepare the putative Sc(AlMe(4))(3), featuring the smallest rare earth metal center, failed.

Complexes [NNN]Ln(AlMe(4))(2) (Ln = Y, La, Nd, Lu) bearing the sterically demanding aryl-substituted triazenido ligand [(Tph)(2)N(3)] (Tph = [2-(2,4,6-iPr(3)C(6)H(2))C(6)H(4)]) can be obtained from homoleptic complexes Ln(AlMe(4))(3) in moderate yields, both via protonolysis with [(Tph)(2)N(3)]H and a salt metathesis reaction pathway utilizing [(Tph)(2)N(3)]K. In the solid state the Y and Lu derivatives are isostructural, with both tetramethylaluminate groups coordinated in an eta(2) fashion, while one of the [AlMe(4)] ligands of the Nd derivative features a distorted eta(2) coordination mode. Due to the high affinity of the triazenido ligand toward the more Lewis-acidic and harder aluminium cation compared to the softer rare-earth metal centres, ligand redistribution is observed in solution and formation of byproduct [(Tph)(2)N(3)]AlMe(2) is prominent. While the monoanionic triazenido ligand coordinates the rare-earth metal centres in an asymmetrical syn/anti fashion, it adopts an almost symmetric syn/syn configuration in the aluminium complex. Attempts were also made to produce putative dimethyl complexes {[(Tph)(2)N(3)]LnMe(2)} (Ln = Y, Lu) via cleavage of the aluminate moieties with diethyl ether. Furthermore, the intrinsic redistribution reactions are proposed to affect the performance of complexes [(Tph)(2)N(3)]Ln(AlMe(4))(2) in isoprene polymerization.