Palladium(II) Complexes of Bis(diphosphene) with the Different Coordination Behavior

Organophosphorus compounds possessing the P−P double-bond character are intriguing materials in coordination chemistry because it is possible to form a variety of coordination modes from the π-bond in addition to...

Electronic structure of (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO and (MePh3P)[NiIII(bdtCl2)2] (bdtCl2 = 3,6-dichlorobenzene-1,2-dithiolate)

High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh3P)2[NiII(bdtCl2)2]·2(CH3)2SO [complex (1)] and (MePh3P)[NiIII(bdtCl2)2] [complex (2)]. Combining the techniques of nickel K- and sulfur K-edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally NiII; that of complex (2) should be formally NiIII, yet it is best described as a combination of Ni2+ and Ni3+, due to the involvement of the non-innocent ligand in the Ni—L bond. A detailed description of Ni—S bond character (σ,π) is presented.

Copper(II) Prevents the Saccarine-Dialkylcyanamide Coupling by Forming Mononuclear (Saccharinate)(Dialkylcyanamide)copper(II) Complexes

The reaction in the system CuII/sacNa(H)/NCNR2 (sacNa(H) = sodium saccharinate (saccharin); R = Me, Et) results in the formation of the complexes [Cu(sac)2(NCNR2)(H2O)2] (R = Me 1, Et 2) instead of the expected products derived from the saccharin–cyanamide coupling. Complexes 1, 2, and hydrate 1·2H2O were characterized by IR, AAS (Cu%), TGA, and also by single-crystal X-ray diffraction for 1 and 1·2H2O. An integrated computational study of model structure 1 in the gas phase demonstrates that the Cu–Ncyanamide and Cu–Nsac coordination bonds exhibited a single bond character, polarized toward the N atom and almost purely electrostatic, with the calculated vertical total energies for the Cu–Ncyanamide and Cu–Nsac of 43.6 and 156.4 kcal/mol, respectively. These data confirmed that the copper(II) completely blocks the nucleophilic centers of ligands via coordination, thus preventing the saccharin–cyanamide coupling.

The α-D-anomer of 2′-deoxycytidine: crystal structure, nucleoside conformation and Hirshfeld surface analysis

β-2′-Deoxyribonucleosides are the constituents of nucleic acids, whereas their anomeric α-analogues are rarely found in nature. Moreover, not much information is available on the structural and conformational parameters of α-2′-deoxyribonucleosides. This study reports on the single-crystal X-ray structure of α-2′-deoxycytidine, C9H13N3O4 (1), and the conformational parameters characterizing 1 were determined. The conformation at the glycosylic bond is anti, with χ = 173.4 (2)°, and the sugar residue adopts an almost symmetrical C2′-endo-C3′-exo twist (^2_3T; S-type), with P = 179.7°. Both values lie outside the conformational range usually preferred by α-nucleosides. In addition, the amino group at the nucleobase shows partial double-bond character. This is supported by two separated signals for the amino protons in the 1H NMR spectrum, indicating a hindered rotation around the C4—N4 bond and a relatively short C—N bond in the solid state. Crystal packing is controlled by N—H...O and O—H...O contacts between the nucleobase and sugar moieties. Moreover, two weak C—H...N contacts (C1′—H1′ and C3′—H3′A) are observed. A Hirshfeld surface analysis was carried out and the results support the intermolecular interactions observed by the X-ray analysis.

The Forgotten Bond : The CBS production of Casino Royale (1954)

In 1954, the US television network CBS broadcast a live studio dramatization of Casino Royale as an instalment of its drama anthology series Climax! Casino Royale was long thought to be “lost” and is still regarded as something of a curio item in the history of James Bond adaptations for the screen. This chapter offers a critical reassessment of the 1954 CBS production of Casino Royale by placing it in the institutional and aesthetic contexts of American television drama in the 1950s. In doing so, it argues that the Americanization of James Bond (played by American actor Barry Nelson) may be seen as part of a strategy of the cultural repositioning of the James Bond character for American consumption.

Branding 007 : Title Sequences in the James Bond Films

The James Bond series has maintained its brand identity through the James Bond character, recurring plot elements, and its film design, in particular the credits sequences of Maurice Binder, Robert Brownjohn, MK12, and Daniel Kleinman. This chapter will examine the work of Binder, who created fourteen of the first eighteen Bond titles and has been rightly singled out as one of a new generation of title designers who utilized modernist aesthetics to create a specific look for the James Bond franchise. The chapter also asks how the digital turn, which coincided with the transition from Binder to Kleinman in the 1990s, has impacted the design and aesthetics of the James Bond title sequences.

Bond Rebooted : The Transnational Appeal of the Daniel Craig James Bond Films

The James Bond films starring Daniel Craig are amongst the most globally successful films of the twenty-first century. The transnational appeal of these films can only be partly explained by their textual attractions, such as the way they play out ideas of British identity. Much of their success depends on the business of Bond, from rights ownership to distribution. Focus group interviews with audiences in continental Europe also reveal an ambivalence about whether the Bond character and the Bond films are perceived as British or American. This ambivalence extends the appeal of the films to different audiences. This chapter therefore provides new insights into Bond’s enduring transnational appeal.