Baryon properties in meson mediums from lattice QCD

We present results for the ground-state mass shifts of octet baryons due to the presence of a medium of pions or kaons from a lattice QCD calculation performed at a single value of the quark mass, corresponding to a pion mass of $m_\pi$ ~ 390 MeV, and a spatial volume V ~ (4fm)^3. We use a canonical approach in which correlators are formed using a single baryon propagator and a fixed number of meson propagators, up to n=9. From the ground-state energies we calculate two- and three-body interaction parameters. We also extract combinations of low-energy constants by comparing our results to tree level chiral perturbation theory at non-zero isospin/kaon chemical potential.Comment: 7 pages, 3 figures, Proceedings of the 31st International Symposium on Lattice Field Theory (Lattice 2013), July 29 - August 3, 2013, Mainz, German

Reactions of isonitriles with [Fe₃(CO)₁₂] and [Ru₃(CO)₁₂] monitored by electrospray mass spectrometry: structural characterisation of [Fe₃(CO)₁₀(CNPh)₂] and [Ru₄(CO)₁₁(μ₃-η²-CNPh)₂(CNPh)]

The reactions of [Fe₃(CO)₁₂] or [Ru₃(CO) ₁₂] with RNC (R=Ph, C₆H₄OMe-p or CH₂SO₂C₆H₄Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe₃(CO)₁₂], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe₃(CO)₁₀(CNPh)₂] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru₃(CO)₁₂] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru₄(CO)₁₁(CNPh)₃] was structurally characterised and has a spiked-triangular Ru₄ core with two of the CNPh ligands coordinated in an unusual μ₃-η² mode. The substitution reactions of [M₃(CO)₁₂] by RNC have been investigated by electrospray mass spectrometry showing up to six COs can be replaced. [Fe₃(CO)₁₀(CNPh)₂] has both PhNC axially on the same Fe atom, and [Ru₄(CO)₁₁(μ₃-η²-CNPh)₂(CNPh)] has a spiked-triangular cluster core with two PhNC ligands in an unusual coordination mode

Synthesis and characterization of nickel(II) maltolate complexes containing ancillary bisphosphine ligands

Cationic nickel(II) complexes containing chelating O,O'-donor maltolate or ethyl maltolate ligands in conjunction with bidentate bisphosphine ligands Ph₂P(CH₂)nPPh₂ were prepared by a one-pot reaction starting from nickel(II) acetate, bisphosphine, maltol (or ethyl maltol), and trimethylamine, and isolated as their tetraphenylborate salts. An X-ray structure determination of [Ni(maltolate)(Ph₂PCH₂CH₂PPh₂)]BPh₄ shows that the maltolate ligand binds asymmetrically to the (slightly distorted) square-planar nickel(II) center. The simplicity of the synthetic method was extended to the synthesis of the known platinum(II) maltolate complex [Pt(maltolate)(PPh₃)₂]BPh₄ which was obtained in high purity

Cycloauration of pyridyl sulphonamides

The pyridyl-2-alkylsulfonamides C₅H₄N(CH₂)nNHSO₂R (n = 1,2; R = Me, Ph or p-C₆H₄Me) and 8-(p-tosylamino)quinoline undergo facile cycloauration reactions with H[AuCl₄] in water, giving metallacyclic complexes coordinated through the pyridyl (or quinolyl) nitrogen atom and the deprotonated nitrogen of the sulfonamide group. The complexes have been fully characterised by NMR spectroscopy, ESI mass spectrometry and elemental analysis. The X-ray crystal structures of two derivatives reveal the presence of non-planar sulfonamide nitrogen atoms. The complexes show low activity against P388 murine leukaemia cells, possibly as a result of their ease of reduction with mild reducing agents

The cycloauration of pyridine-2-thiocarboxamide ligands

Reactions of H[AuCl₄] with N-substituted 2-pyridine thiocarboxamide ligands 2-(C₅H₄N)C(S)NHR (R= p-C₆H₄Me, CH₂Ph, Me, p-C₆H₄OMe) gave cycloaurated derivatives {(C₅H₄N)C(S)NR}AuCl₂, with the ligand bonded as the thiol tautomer through the deprotonated SH group and the pyridine N atom to give a five-membered metallacyclic ring. The X-ray structure determination of the R = CH₂Ph derivative shows a square-planar gold(III) complex that dimerises in the solid state by weak Au...S intermolecular interactions. In contrast, in the reaction of H[AuCl₄] with 2-(C₅H₄N)C(S)NHR where R = 2-pyridyl, the ligand was oxidised to give a 1,2,4-thiadiazolo[2,3-a]pyridinium heterocyclic ring that was crystallographically characterised

(p -Cymene)thioglycollatoruthenium(II) dimer; a complex with an ambi-basic S,O-donor ligand

The title compound was prepared from the (p-cymene)ruthenium chloride dimer and thioglycollic acid. The structure is a centrosymmetric dimer bridged by the soft-base S atoms, with the hard-base O atoms of the carboxylate group chelating to form a five-membered twisted-ring. The coordination of the ruthenium atoms is completed by a η6-p-cymene ligand, giving an 18-electron count. The Ru–S bonds are essentially equal at 2.396(1) Å

Five-coordinate gold(III) complexes of the Kläui ligands [(η⁵-C₅H₅)Co{P(O)(OR)₂}₃]− (R°=°Me, Et)

The reactions of cycloaurated gold(III) dichloride complexes [LAuCl₂] (L°=°2-C₆H₄CH₂NMe₂ or 2-C₆H₄PPh₂ NPh) with monoanionic tripodal oxygen donor Kläui ligands [(η⁵-C₅H₅)Co{P(O)(OR) ₂}₃]− (R°=°Me or Et) results in the formation of cationic gold(III) salts [LAu{OP(OR) ₂}₃Co(η⁵-C₅H₅)]+. An X-ray structure determination on [(2-C₆H₄PPh₂ NPh)Au{OP(OR) ₂}₃Co(η⁵-C₅H₅)]BF₄shows that the Kläui ligand coordinates strongly to the gold through two oxygen atoms, and weakly through the third, giving the gold(III) a distorted square pyramidal geometry. This is the first structurally characterised example of this geometry for gold(III) with ligands other than those containing rigid bipyridine or phenanthroline backbones. In solution at room temperature there is rapid interchange (on the NMR timescale) between the oxygen atoms of the Kläui ligands, which is frozen out on cooling

Synthesis and reactivity of gold(III) complexes containing cycloaurated iminophosphorane ligands

Transmetallation reactions of ortho-mercurated iminophosphoranes (2-ClHgC₆H₄)Ph₂P NR with [AuCl₄]⁻ gives new cycloaurated iminophosphorane complexes of gold(III) (2-Cl₂AuC₆H₄)Ph₂P NR [R = (R,S)- or (S)-CHMePh, p-C₆H₄F, tBu], characterised by NMR and IR spectroscopies, ESI mass spectrometry and an X-ray structure determination on the chiral derivative R = (S)-CHMePh. The chloride ligands of these complexes can be readily replaced by the chelating ligands thiosalicylate and catecholate; the resulting derivatives show markedly higher anti-tumour activity versus P388 murine leukaemia cells compared to the parent chloride complexes. Reaction of (2-Cl₂AuC₆H₄)Ph₂P NPh with PPh₃ results in displacement of a chloride ligand giving the cationic complex [(2-Cl(PPh₃)AuC₆H₄)Ph₂P NPh]⁺, indicating that the P N donor is strongly bonded to the gold centre

Cycloaurated triphenylphosphine-sulfide and –selenide

The first examples of cycloaurated phosphine sulfides and triphenylphosphine selenide have been synthesised; these complexes are fairly rare examples of gold(III) complexes with potentially reducing sulfur- and selenium-donor ligands. The cycloaurated complex (AuCl₂ (2-C₆H₄P(S)Ph₂) was synthesised in good yield by transmetallation of the organomercury precursor Hg(2-C₆H₄P(S)Ph₂)₂ with Me₄N[AuCl₄]. A route to the chloro-mercury analogue ClHg(2-C₆H₄P(S)Ph₂) was developed by reaction of the cyclomanganated triphenylphosphine sulfide (CO)₄Mn(2-C₆H₄P(S)Ph₂) with HgCl₂; this mercury substrate was also used in the synthesis of AuCl₂(2-C₆H₄P(S)Ph₂). The cycloaurated triphenylphosphine selenide complex AuCl₂(2-C₆H₄P(Se)Ph₂) was synthesised by an analogous methodology using the new phosphine selenide Hg(2-C₆H₄P(Se)Ph₂)₂ [prepared from Hg(2-C₆H₄PPh₂)₂ and elemental Se under sonication]. The phosphonamidic analogue AuCl₂(2-C₆H₄P(S)(Net₂)₂) has also been synthesised from PhP(S)(Net₂)₂via lithiation and mercuration. X-Ray crystal structures of several compounds are reported, and show the presence of puckered ring systems