Brian P. Johnson

Structures and Properties of Spherical 90-Vertex Fullerene-Like Nanoballs

By applying the proper stoichiometry of 1:2 to [Cp(R)Fe(eta(5)-P(5))] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH(3)CN and solvents like CH(2)Cl(2), 1,2-Cl(2)C(6)H(4), toluene, and THF, nine spherical giant molecules having the simplified general formula [Cp(R)Fe(eta(5)-P(5))]@[{Cp(R)Fe(eta(5)-P(5))}(12){CuX}(25)(CH(3)CN)(10)] (Cp(R)=eta(5)-C(5)Me(5) (Cp*); eta(5)-C(5)Me(4)Et (Cp(Et)); X=Cl, Br) have been synthesized and structurally characterized. The products consist of 90-vertex frameworks consisting of non-carbon atoms and forming fullerene-like structural motifs. Besides the mostly neutral products, some charged derivatives have been isolated. These spherical giant molecules show an outer diameter of 2.24 (X=Cl) to 2.26 nm (X=Br) and have inner cavities of 1.28 (X=Cl) and 1.20 nm (X=Br) in size. In most instances the inner voids of these nanoballs encapsulate one molecule of [Cp*Fe(eta(5)-P(5))], which reveals preferred orientations of pi-pi stacking between the cyclo-P(5) rings of the guest and those of the host molecules. Moreover, pi-pi and sigma-pi interactions are also found in the packing motifs of the balls in the crystal lattice. Electrochemical investigations of these soluble molecules reveal one irreversible multi-electron oxidation at E(p)=0.615 V and two reduction steps (-1.10 and -2.0 V), the first of which corresponds to about 12 electrons. Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu(2+) species are involved.

cyclo-P4 Building Blocks: Achieving Non-Classical Fullerene Topology and Beyond

Abstract The cyclo‐P4 complexes [CpRTa(CO)2(η4‐P4)] (CpR: Cp′′=1,3‐C5H3tBu2, Cp′′′=1,2,4‐C5H2tBu3) turned out to be predestined for the formation of hollow spherical supramolecules with non‐classical fullerene‐like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32‐vertex core of solely four‐ and six‐membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut‐ or pear‐like shapes and outer diameters in the range of 2–2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp′′′ ligands at tantalum are soluble in CH2Cl2. NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp′′′ ligand. In addition, a 2D coordination polymer was obtained and structurally characterized.

Untersuchungen zur Darstellung von [CpxSb{M(CO)5}2] (Cpx = Cp, Cp*; M = Cr, W)

Die Reaktion von CpSbCl2 mit [Na2{Cr2(CO)10}] fuhrt zum Chlorostibinidenkomplex [ClSb{Cr(CO)5}2(thf)] (1), wohingegen sich bei der Umsetzung von CpSbCl2 mit [Na2{W2(CO)10}] die Komplexe [ClSb{W(CO)5}3] (2), [Na(thf)][Cl2Sb{W(CO)5}2] (3), [ClSb{W(CO)5}2(thf)] (4) und [Sb2{W(CO)5}3] (5) bilden. Die Darstellung des Stibinidenkomplexes [CpSb{Cr(CO)5}2] (6) gelingt durch die Reaktion von [ClSb{Cr(CO)5}2] mit NaCp, wahrend sein Cp*-substituiertes Analogon [Cp*Sb{Cr(CO)5}2] (7) direkt durch Metathese von Cp*SbCl2 mit [Na2{Cr2(CO)10}] zuganglich wird. Die Produkte 2, 3, 4 und 7 werden zusatzlich zu ihren spektroskopischen Daten durch Kristallstrukturanalysen charakterisiert.

Formation of Spherical Giant Molecules and Dynamic Behaviour of Supramolecular Assemblies Based on Pn-Ligand Complexes

We report herein on our concept of using En-ligand complexes (E = P, As) as linking units for the creation of novel supramolecular ensembles. The reaction of these complexes with Group 11 metal salts of coordinating anions leads to the formation of insoluble oligomers, 1D and 2D polymers as well as soluble spherical nanoscaled clusters. In contrast, the reaction of En-ligand complexes with Group 11 metal salts of weakly coordinating anions yields soluble oligomers and polymers, which display monomer-oligomer equilibria in solution.

Complexes with a Metal Phosphorus Triple Bond – a Novel Class of Highly Reactive Compounds

A novel approach to highly reactive phosphido complex intermediates of the type [LnM=P→M′(CO)5] (M′ = Cr, W) is achieved via the Cp* migration from a σ-bound situation at a P atom in a phosphinidene complex [Cp*P{W(CO)5}2] to the η5-coordination at the transition metal. Consequently those compounds show a high “side-on” reactivity. Their reaction behavior with phosphaalkynes, alkynes and nitriles leads to novel metala-phosphaheterocycles. Furthermore, the use of the corresponding As analogue [Cp*As{W(CO)5}2] yields via thermolysis reaction the tetranuclear tungsten clusters, which indicate besides the formation of the triple bond intermediate [Cp*(CO)2W[As→W(CO)5] the occurrence of a second Cp* eliminated intermediate [As{W(CO)5}2].

Complexes with a Metal-Phosphorus Triple Bond as Versatile Building Blocks in Coordination and Organometallic Chemistry

Trapping reactions of the phosphido complex intermediate [Cp*(CO) 2 W L P M W(CO) 5 ], generated by thermolysis of [Cp*P{W(CO) 5 } 2 ] 1 , occur via [2 + 2] cycloaddition reactions with P 4 , phosphaalkynes, alkynes, and [CpMo(CO) 2 ] 2 , respectively. However, with nitriles, insertion reactions into the P--C bond of 1 are observed already at room temperature to give novel P-containing heterocycles. Furthermore, irradiation of 1 gives the tetrahedral complex [Cp*(CO) 6 W 2 }( w -H)( w , m 2 -P 2 ){W(CO) 5 } 2 ], which indicates that besides the formation of the triple-bond intermediate [Cp*(CO) 2 W L P M W(CO) 5 ] a second Cp* elimination intermediate of the type [P{W(CO) 5 } 2 ] occurs.

The Nozoe Autograph Books Project: An Assessment

Bonding beyond Borders is a fitting title to the Nozoe Autograph Books project, as the books and their publication involved innumerable contributors from around the globe all in the spirit of personal collaboration. The editors of this project share details of how the project came into being and give their own personal assessment of what it has become and what it means.

Ushering in a new era

highlights” journal, publishing critical overviews of topical areas of chemistry that are written from a personal perspective. It is this personalized quality that makes the journal unique from other review journals and brings authors and readers together in approaching a pair of all-encompassing questions: What areas are of the most imminent relevance to researchers’ endeavors across multiple disciplines, and what challenges do researchers face in reaching the next level of discovery? While The Chemical Record has undergone a number of positive developments over the past few years, its position as an international and interdisciplinary forum for addressing these big-picture questions has only gotten stronger. During this year, fittingly within the International Year of Chemistry 2011, The Chemical Record has been able to celebrate a series of editorial highlights of its own. There have been several recent developments in and around The Chemical Record that have been truly inspiring. After the publishing responsibility for The Chemical Record was transferred two years ago to the offices of Wiley-VCH, society publishers of Angewandte Chemie and Chemistry-An Asian Journal, the cooperation between the publisher and the owner societies of The Chemical Record was intensified toward mapping the editorial progress of the journal. During these two years, and even starting well before that, the journal was set on a new path forward, with the Chemical Society of Japan (CSJ) taking the leading society role. The Chemical Record is now an official journal of the Chemical Society of Japan. To top it all off, the Chemical Society of Japan and Wiley-VCH have recently strengthened their collaboration on The Chemical Record through the signing of a new publishing agreement during the recent Angewandte Symposium in June 2011 in Tokyo (Figure 1). This signing came just days before it was announced that TCR had received its highest Impact Factor ever: 4.604 for 2010, which is an eye-catching 19% increase over its 2009 Impact Factor of 3.862. This increase represents the journal’s third in a row. The recent trend of a sharply rising Impact Factor for The Chemical Record is the culmination of several years of dedicated effort from the scientists behind the journal, not least of which through the tireless commitment of immediate past Editor-inChief Koji Nakanishi and current Editor-in-Chief Hisashi Yamamoto, who succeeded Professor Nakanishi in 2010 and has already made outstanding and creative contributions. To expand the horizons of the journal even further, an infusion of extremely talented scientists joined the Editorial Board and the International Advisory Board at the beginning of 2011. The members of the Editorial Board (Figure 2) are active in each of