Unusual structure, bonding and properties in a californium borate.
نویسندگان
چکیده
The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.
منابع مشابه
استفاده از عوامل پیوندی بورات استری در پیشرانه های جامد
Bonding agents are one of the most important components of solid propellants that enhance the interaction between solid particles and binders. Many bonding agents have been reported so far and sufficient laboratory studies have been carried out on their mechanism of action, including, hydantoin, isocyanorathe, vinyl ether, base-shif, etc. Borate esters are other group of bonding agents that mos...
متن کاملEmergence of californium as the second transitional element in the actinide series
A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of calif...
متن کاملStructural Investigation, Physical and Optical Properties of Mixed Alkali Bismuth Borate Glasses
Lead free, eco-friendly bismuth borate glasses doped with alkali oxides of composition xLi2O+(30-x)Na2O+55B2O3+15Bi2O3 (x = 5,10,15,20,25) were prepared by melt quenching technique. Amorphous nature of glasses was confirmed by X-ray diffraction. Density measurements were carried out at room temperature by standard principle of Archimedes with Xylene as an immersion liquid. The non-linear ...
متن کاملTheoretical study of tetrahedrane derivatives
Tetrahedrane is most strained and the smallest cage compound. It attracts organic chemists because ofits unusual bonding nature and highly symmetrical structure. However, many efforts to isolate theparent tetrahedrane have been unsuccessful because of the high reactivity and very short lifetimecaused by the strain in this molecule. Modeling of molecules for determination of structuralproperties...
متن کاملElectronic Structure, Biological Activity, Natural Bonding Orbital (NBO) and Non-Linear Optical Properties (NLO) of Poly-Functions Thiazolo [3,2-a]Pyridine Derivatives. DFT Approach
The optimized structures of studied compounds 23-28 are non planner with the two phenyl at C3 and C9 are out of the molecular plane of thiazolo[3,2-a]pyridine as indicated from a dihedral angles of 710 and 1160 respectively, using DFT-B3LYP method with 6-311G(d,p) as basis set. The natural bonding orbital (NBO) analysis of the parent molecule 23 have been analyzed in terms of the hybridization ...
متن کاملذخیره 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 ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Nature chemistry
دوره 6 5 شماره
صفحات -
تاریخ انتشار 2014