Gold(III) six-membered N^C^N pincer complexes: synthesis, structure, reactivity and theoretical calculations.

The first six-membered gold(III) N^C^N pincer complex was obtained in good yield, under very mild conditions, by transmetalation of [Hg(κC-N^C^N)Cl] (N^CH^N = 1,3-bis(pyridin-2-ylmethyl)benzene, HL(1)) with Na[AuCl(4)]. The X-ray crystal structure of [Au(N^C^N)Cl][PF(6)] showed that the fused six-membered metallacycles each exist in a strongly puckered boat conformation. As shown by the (1)H NMR spectra in various solvents, the same structure is also retained in solution: no inversion of the six-membered metallacycles is observed in DMSO up to 95 °C.

Large effect of a small substitution: competition of dehydration with charge retention and coulomb explosion in gaseous [(bipy(R))Au(mu-O)2Au(bipy(R))]2+ dications.

Dinuclear gold(III) clusters with a rhombic Au(2)O(2) core and 2,2'-bipyridyl ligands substituted in the 6-position (bipy(R)) are examined by tandem mass spectrometry. Electrospray ionization of the hexafluorophosphate salts affords the complexes [(bipy(R))Au(mu-O)(2)Au(bipy(R))](2+) as free dications in the gas phase. The fragmentation behavior of the mass-selected dications is probed by means of collision-induced dissociation experiments which reveal an exceptionally pronounced effect of substitution.

Chemistry, antiproliferative properties, tumor selectivity, and molecular mechanisms of novel gold(III) compounds for cancer treatment: a systematic study.

The antiproliferative properties of a group of 13 structurally diverse gold(III) compounds, including six mononuclear gold(III) complexes, five dinuclear oxo-bridged gold(III) complexes, and two organogold(III) compounds, toward several human tumor cell lines were evaluated in vitro using a systematic screening strategy. Initially all compounds were tested against a panel of 12 human tumor cell lines, and the best performers were tested against a larger 36-cell-line panel. Very pronounced antiproliferative properties were highlighted in most cases, with cytotoxic potencies commonly falling in the low micromolar--and even nanomolar--range.

Reactivity of 1,3-bis(2-pyridyl)benzene, N--CH--N, with gold(III) chlorides: salts, adducts and cyclometalated pincer derivatives. Crystal and molecular structures of [HN--CH--N][AuCl4], [Au(N--C--N)Cl][PF6] and [Au(N--C--N)Cl(PPh3)2][PF6].

The reaction of 1,3-bis(2-pyridyl)benzene, N--CH--N, with H[AuCl(4)] has been studied under different conditions. Mono- ([N--CH--NH][AuCl(4)]) and di-protonated salts ([HN--CH--NH][AuCl(4)](2)), as well as an adduct, [(N--CH--N)(AuCl(3))(2)], have been isolated. Very rare cyclometalated pincer derivatives, [Au(N--C--N)Cl](+) have been obtained as different salts, either by transmetallation from the corresponding mercury(ii) derivative, [Hg(N--C--N)Cl], or by direct C-H activation.

Structural characterization, solution studies, and DFT calculations on a series of binuclear gold(III) oxo complexes: relationships to biological properties.

A series of structurally related oxo-bridged binuclear gold(III) compounds, [Au2(mu-O)2(N;N)2](PF6)2, where N;N is 2,2'-bipyridine or a substituted 2,2'-bipyridine, have recently been shown to exhibit appreciable stability under physiological-like conditions and to manifest important antiproliferative effects toward selected human tumor cell lines (J. Med. Chem.