Cycloaurated GoId (III) complexes- Possible alternatives to cisplatin?

The serendipitous discovery of the anti-tumour activity of cisplatin [cis-PtCI₂(NH₃)₂] in 1969 has led to increased interest in the development of new metal-based anti-cancer drugs. However, regardless of the large numbers of new metal-containing compounds generated, many of which demonstrate anti-tumour activity, cisplatin still remains one of the most widely used anti-tumour drugs in the western world

Generalized gravitational entropy without replica symmetry

We explore several extensions of the generalized entropy construction of Lewkowycz and Maldacena, including a formulation that does not rely on preserving replica symmetry in the bulk. We show that an appropriately general ansatz for the analytically continued replica metric gives us the flexibility needed to solve the gravitational field equations beyond general relativity. As an application of this observation we study Einstein-Gauss-Bonnet gravity with a small Gauss-Bonnet coupling and derive the condition that the holographic entanglement entropy must be evaluated on a surface which extremizes the Jacobson-Myers entropy. We find that in both general relativity and Einstein-Gauss-Bonnet gravity replica symmetry breaking terms are permitted by the field equations, suggesting that they do not generically vanish.Comment: 24 pages, 3 figures. v3: fixed some more typos, v2: fixed minor typo

A six-coordinate aryl-germanium complex formed by the Kläui ligand

PhGeCl₃ reacts with Na{[OP(OEt)₂]₃CoCp} to give the six-coordinate complex PhCl₂Ge{[OP(OEt)₂]₃CoCp}, characterised spectroscopically and by an X-ray crystal structure determination which showed a firmly-attached tridentate ligand [Ge–O 1.973(2) Å]

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

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

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

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

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

The Final Merger of Black-Hole Binaries

Recent breakthroughs in the field of numerical relativity have led to dramatic progress in understanding the predictions of General Relativity for the dynamical interactions of two black holes in the regime of very strong gravitational fields. Such black-hole binaries are important astrophysical systems and are a key target of current and developing gravitational-wave detectors. The waveform signature of strong gravitational radiation emitted as the black holes fall together and merge provides a clear observable record of the process. After decades of slow progress, these mergers and the gravitational-wave signals they generate can now be routinely calculated using the methods of numerical relativity. We review recent advances in understanding the predicted physics of events and the consequent radiation, and discuss some of the impacts this new knowledge is having in various areas of astrophysics.Comment: 57 pages; 9 figures. Updated references & fixed typos. Published version is at http://www.annualreviews.org/doi/abs/10.1146/annurev.nucl.010909.08324

Black-hole binaries, gravitational waves, and numerical relativity

Understanding the predictions of general relativity for the dynamical interactions of two black holes has been a long-standing unsolved problem in theoretical physics. Black-hole mergers are monumental astrophysical events, releasing tremendous amounts of energy in the form of gravitational radiation, and are key sources for both ground- and space-based gravitational-wave detectors. The black-hole merger dynamics and the resulting gravitational waveforms can only be calculated through numerical simulations of Einstein's equations of general relativity. For many years, numerical relativists attempting to model these mergers encountered a host of problems, causing their codes to crash after just a fraction of a binary orbit could be simulated. Recently, however, a series of dramatic advances in numerical relativity has allowed stable, robust black-hole merger simulations. This remarkable progress in the rapidly maturing field of numerical relativity, and the new understanding of black-hole binary dynamics that is emerging is chronicled. Important applications of these fundamental physics results to astrophysics, to gravitational-wave astronomy, and in other areas are also discussed.Comment: 54 pages, 42 figures. Some typos corrected & references updated. Essentially final published versio