New ligand platforms featuring boron-rich clusters as organomimetic substituents.

نویسنده

  • Alexander M Spokoyny
چکیده

200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the "space race" while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules-a phenomenon best described as "organomimetic". Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

All-boron aromatic clusters as potential new inorganic ligands and building blocks in chemistry

Small boron clusters as individual species in the gas phase are reviewed. While the family of known boron compounds is rich and diverse, a large body of hitherto unknown chemistry of boron has been recently identified. Free boron clusters have been recently characterized using photoelectron spectroscopy and ab initio calculations, which have established the planar or quasi-planar shapes of smal...

متن کامل

Boronyl chemistry: the BO group as a new ligand in gas-phase clusters and synthetic compounds.

Boronyl (BO) is a monovalent σ radical with a robust B≡O triple bond. Although BO/BO(-) are isovalent to CN/CN(-) and CO, the chemistry of boronyl has remained relatively unknown until recently, whereas CN/CN(-) and CO are well-known inorganic ligands. Further analogy may be established for BO versus H or Au ligands, which are all monovalent σ radicals. This Account intends to provide an overvi...

متن کامل

Intramolecular frustrated lewis pairs: formation and chemical features.

Intramolecular vicinal and geminal frustrated Lewis pairs (FLPs) featuring bulky substituents at phosphorus or nitrogen and strongly electron-withdrawing bulky pentafluorophenyl substituents at boron undergo a variety of addition and/or activation reactions with small molecules. A number of examples of such reactions are presented and discussed, among them the FLP activation of dihydrogen to gi...

متن کامل

Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants.

We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B12(OCH2Ar)12 (Ar = Ph or C6F5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized thr...

متن کامل

Transition-metal-centered monocyclic boron wheel clusters (M©Bn): a new class of aromatic borometallic compounds.

Atomic clusters have intermediate properties between that of individual atoms and bulk solids, which provide fertile ground for the discovery of new molecules and novel chemical bonding. In addition, the study of small clusters can help researchers design better nanosystems with specific physical and chemical properties. From recent experimental and computational studies, we know that small bor...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Pure and applied chemistry. Chimie pure et appliquee

دوره 85 5  شماره 

صفحات  -

تاریخ انتشار 2013