From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co38As12(CO)50]4.

The cluster [Co38As12(CO)50]4- was obtained by pyrolysis of [Co6As(CO)16]-. The metal cage features a closed-packed core inside a Co/As shell that progressively deforms from a cubic face-centered symmetry. The redox and acid-base reactivities were determined by cyclic voltammetry and spectrophotometric titrations. The calculated electron density revealed the shell-constrained distribution of the atomic charges, induced by the presence of arsenic.

A BPA Approach to the Shroud of Turin.

An investigation into the arm and body position required to obtain the blood pattern visible in the image of the Shroud of Turin was performed using a living volunteer. The two short rivulets on the back of the left hand of the Shroud are only consistent with a standing subject with arms at a ca 45° angle. This angle is different from that necessary for the forearm stains, which require nearly vertical arms for a standing subject. The BPA of blood visible on the frontal side of the chest (the lance wound) shows that the Shroud represents the bleeding in a realistic manner for a standing position while the stains at the back-of a supposed postmortem bleeding from the same wound for a supine corpse-are totally unrealistic. Simulation of bleeding from the nail wounds contacting wood surfaces yielded unclear results.

Synthesis, reactivity, electrochemical behavior, and crystal structure of a family of multivalent metal carbido-carbonyl clusters based on the Rh10(C)2Au(4-6) framework.

Six metal carbido-carbonyl clusters have been isolated and recognized as members of a multivalent family based on the dioctahedral Rh(10)(C)(2) frame, with variable numbers of CO ligands, AuPPh(3) moieties, and anionic charge: [Rh(10)(C)(2)(CO)(x)(AuPPh(3))(y)](n-) (x = 18, 20; y = 4, 5, 6; n = 0, 1, 2). Anions [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)](-) ([2](-)) and [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)](2-) ([2](2-)) have been obtained by the reduction of [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(4)] (2) under N(2), while [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(5)](-) ([3](-)) was obtained from [Rh(10)(C)(2)(CO)(20)(AuPPh(3))(4)] (1) by reduction under a CO atmosphere. [3](-) can be better obtained by the addition of AuPPh(3)Cl to [2](2-). [Rh(10)(C)(2)(CO)(18)(AuPPh(3))(6)] (4) is obtained from [3](-) and 2 as well by the reduction and subsequent addition of AuPPh(3)Cl. The molecular structures of [2](2-) ([NBu(4)](+) salt), [3](-) ([NMe(4)](+) salt), and 4 have been determined by single-crystal X-ray diffraction. The redox activities of complexes 1, 2 and [3](-) have been investigated by electrochemical and electron paramagnetic resonance (EPR) techniques. The data from EPR spectroscopy have been accounted for by theoretical calculations.

Four tetrairidium carbonyl clusters linked by six diphosphino ligands: synthesis and X-ray structure of [{Ir(4)(CO)(9)}(4)(dppmb)(6)] (dppmb = 1,4-bis(diphenylphosphinomethyl)benzene.

Tetrairidium carbonyl clusters are potentially useful connectors for multidimensional functionalized frameworks with organic bis-phosphines as linkers. The reaction of Ir(4)(CO)(12) and 1,4-bis(diphenylphosphinomethyl)benzene produces an oligomeric cyclic structure, made of 4 connectors and 6 linkers, a possible intermediate in the formation of three dimensional networks.

A traditional synthetic method, and a new structural motif, for molybdenum-gold clusters: synthesis and solid-state structure of Au8{Mo(CO)5}4(PPh3)4.

The neutral cluster [Au8Mo4(CO)20(PPh3)4] was synthesized in low yield from [AuCl(PPh3)] and [Mo2(CO)10]2- in acetonitrile at room temperature. The cluster was characterized by X-ray analysis, IR, and 31P NMR spectroscopy. Its solid-state structure consists of four Au(3)Mo tetrahedral units, fused by four Au atoms in a ring. The average bond lengths are Au-Au 2.77 Angstrom and Mo-Au 2.93 Angstrom. The internal angles of the planar square ring are very close to 90 degrees.

Antigravity hills are visual illusions.

Antigravity hills, also known as spook hills or magnetic hills, are natural places where cars put into neutral are seen to move uphill on a slightly sloping road, apparently defying the law of gravity. We show that these effects, popularly attributed to gravitational anomalies, are in fact visual illusions. We re-created all the known types of antigravity spots in our laboratory using tabletop models; the number of visible stretches of road, their slant, and the height of the visible horizon were systematically varied in four experiments. We conclude that antigravity-hill effects follow from a misperception of the eye level relative to gravity, caused by the presence of either contextual inclines or a false horizon line.

Electron density of semi-bridging carbonyls. Metamorphosis of CO ligands observed via experimental and theoretical investigations on [FeCo(CO)(8)](-).

The electron density distribution in a transition-metal dimer containing a semibridging carbonyl is determined through experimental X-ray diffraction and quantum chemical computations. The changes occurring during the evolution from terminal to bridging coordinations are described by a "structure-correlation-like" approach and by a theoretical investigation along the conversion path. The smooth continuum of conformations observed in the solid state is explained in terms of the mutual interplay of direct M-M and M-CO and indirect M- - -M and M- - -C interactions, which can be characterized by interatomic delocalization indexes, within the framework of Quantum Theory of Atoms in Molecules.

Iron-Rhodium and Iron-Iridium Mixed-Metal Nitrido-Carbonyl Clusters. Synthesis, Characterization, Redox Properties, and Solid-State Structure of the Octahedral Clusters [Fe(5)RhN(CO)(15)](2)(-), [Fe(5)IrN(CO)(15)](2)(-), and [Fe(4)Rh(2)N(CO)(15)](-). Infrared and Nuclear Magnetic Resonance Spectroscopic Studies on the Interstitial Nitride.

The cluster [Fe(5)RhN(CO)(15)](2)(-) was synthesized in 40% yield from [Fe(4)N(CO)(12)](-) and [Rh(CO)(4)](-) in refluxing tetrahydrofuran, whereas the analogous anion [Fe(5)IrN(CO)(15)](2)(-) was prepared in CH(3)CN at room temperature from [Fe(6)N(CO)(15)](3)(-) and [Ir(C(8)H(14))(2)Cl](2); the yields are higher than 60%. The monoanion [Fe(4)Rh(2)N(CO)(15)](-) was obtained in 70% yield from [Fe(5)RhN(CO)(15)](2)(-) and hydrated RhCl(3). The solid-state structures of the three anions were determined on their [PPh(4)](+) salts: the six metal atoms are arranged in octahedral cages and are coordinated to 3 edge-bridging and 12 terminal carbonyl ligands and to a &mgr;(6)-N ligand. The Rh and Ir atoms have less terminal COs than Fe, in order to equalize the excess electrons at the d(9) metal centers. The two rhodium atoms in [Fe(4)Rh(2)N(CO)(15)](-) are directly bound. The (15)N NMR spectra of the three compounds have been recorded; the signals of the nitride ligands were found at delta = 514 ppm for the dianions and 470 ppm for [Fe(4)Rh(2)N(CO)(15)](-); any group 9 atom shifts the resonance of nitrogen to higher fields. The coupling constants J((15)N-(103)Rh) are 8-9 Hz. The vibrational patterns of the metal cores have been interpreted on the basis of an idealized M(6) octahedral arrangement, subsequently modified by the perturbations given by different atomic masses and M-M stretching force constants. The motions of the nitrogen are related to the idealized symmetry of the cage; the M-N force constant values depend on the type of metal and on the charge of the anion. The dianions [Fe(5)MN(CO)(15)](2)(-) can be electrochemically oxidized at -20 degrees C to their short-lived monoanions, which can be characterized by EPR spectroscopy. In contrast, the cluster [Fe(4)Rh(2)N(CO)(15)](-) undergoes a single-step 2-electron reduction to the partially stable trianion [Fe(4)Rh(2)N(CO)(15)](3)(-), which was also characterized by EPR spectroscopy. The Fe-Rh nitride clusters are active catalysts for the hydroformylation of 1-pentene, but display low selectivity (35-65%) in n-hexanal and are demolished under catalytic conditions.