Publisher Summary This chapter discusses the field of transition-metal complexes of isocyanides developed slowly over more than a century to a respectable subarea in coordination chemistry and which, in the process, seems to have attracted very little attention. The valence-bond pictures for an isocyanide and carbon monoxide and for metal complexes of these ligands emphasize the similarities of both the ligands and their complexes. The insertion of a carbonyl group into a metal–alkyl or metal–aryl bond and the reverse reaction involving decarbonylation of an acyl complex have been studied from both the synthetic and mechanistic points of view. The reactions of nucleophilic reagents with cationic and uncharged metal carbonyl complexes have received much attention in the past, and it is not surprising that these studies have now been extended to isocyanide metal complexes. Perhaps the greatest excitement in the field of metal isocyanide complex chemistry has been generated by the observation that a variety of protonic substances (alcohols, thiols, amines, and hydrazine) add to the coordinated isocyanide ligand. A number of chemists have been interested in the chemistry of cobinamine and cobaloxime complexes of several ligands, including isocyanides.

Transition Metal-lsocyanide Complexes

Publisher Summary The chapter discusses facets associated with the nature of the interactions between acetylenes and transition metals and to the insertion reactions of complexes closely related to catalysis. Although only scattered data are available, attempts were made to give a consistent interpretation of the relativities of coordinated acetylene in terms of a qualitative molecular orbital picture. Studies on elementary reactions of acetylenes with metal complexes are now beginning to shed some light on the nature of activation caused by complication. This activation is not a simple process. Many low-valent d 8 -d 10 metal complexes and also some early transition metal compounds with higher oxidation state are capable of activating acetylenes. In the former complexes, interaction would lead to activation of an n 2- acctylcne ligand to an η-acetylene having some radical as well as some anionic character. The chapter also focuses on the complex chemistry and catalytic oligomerizations of allene. It also describes the importance of the role played by auxiliary ligands of transition metals in determining the paths of catalytic oligomerizations. In general the thermal reaction of allene gives a complex mixture of dimers, trimers, and higher oligomers including small amounts of spiro compounds.

Acetylene and Allene Complexes: Their Implication in Homogeneous Catalysis

Publisher Summary This chapter discusses the chemistry of nitrogen fixation and models for the reactions of nitrogenase The interest in nitrogen fixation for the inorganic chemist is to try to understand, using simple compounds, what nature does so comparatively effortlessly within the enzyme, nitrogenase This is of particular value considering the increasing demand for nitrogenous fertilizers, and the vast industrial expenditure of energy in producing ammonia The literature of chemical nitrogen fixation, even excluding that related to the Haber process, is now considerable The mechanisms of reaction of coordinated dinitrogen are a matter of dispute There are several proposals extant, chemical and biological, and these are espoused by their progenitors with varying degrees of fervor However, there is now sufficient chemistry available for us to make preliminary judgments concerning the validity of the various proposals

The Chemistry of Nitrogen Fixation and Models for The Reactions of Nitrogenase

Zerovalent transition metal complexes of organic isocyanides

On-chip micro-supercapacitors (MSCs) are important Si-compatible power-source backups for miniaturized electronics. Despite their tremendous advantages, current on-chip MSCs require harsh processing conditions and typically perform like resistors when filtering ripples from alternating current (AC). Herein, we demonstrated a facile layer-by-layer method towards on-chip MSCs based on an azulene-bridged coordination polymer framework (PiCBA). Owing to the good carrier mobility (5×10−3 cm2 V−1 s−1) of PiCBA, the permanent dipole moment of azulene skeleton, and ultralow band gap of PiCBA, the fabricated MSCs delivered high specific capacitances of up to 34.1 F cm−3 at 50 mV s−1 and a high volumetric power density of 1323 W cm−3. Most importantly, such MCSs exhibited AC line-filtering performance (−73° at 120 Hz) with a short resistance–capacitance constant of circa 0.83 ms.

Coordination Polymer Framework Based On-Chip Micro-Supercapacitors with AC Line-Filtering Performance

Isocyanide-nickel(0) and -palladium(0) complexes involving unsaturated ligands

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Isocyanide-nickel(0) and -palladium(0) complexes involving unsaturated ligands