Several new donor-acceptor adducts of niobium and tantalum pentaazide with N-donor ligands have been prepared from the pentafluorides by fluoride-azide exchange with Me3SiN3 in the presence of the corresponding donor ligand. With 2,2'-bipyridine and 1,10-phenanthroline, the self-ionization products [MF4(2,2'-bipy)2](+)[M(N3)6](-), [M(N3)4(2,2'-bipy)2](+)[M(N3)6](-) and [M(N3)4(1,10-phen)2](+)[M(N3)6](-) were obtained. With the donor ligands 3,3'-bipyridine and 4,4'-bipyridine the neutral pentaazide adducts (M(N3)5)2⋅L (M=Nb, Ta; L=3,3'-bipy, 4,4'-bipy) were formed.

Abstract. The complexes [MF 4 (py) 6 ]·½CH 3 CN (M = Nb, Ta) were obtained from niobium and tantalum pentafluoride by reaction with the donor ligands pyridine (py), 2,2Ј-bipyridine (2,2Ј-bipy), and bis(diphenylphosphanyl) ethane (dppe) in acetonitrile solution. The complexes were characterized by their vibrational spectra and, in case of the pyridine and dppe adducts, by their crystal structure. The pairs of corresponding

The problem of preparing energetic, exclusively mono-azolyl substituted hydridoborate anions in high yield and purity from [BH ] and nitroazoles by hydrogen elimination was overcome by reacting the corresponding nitroazolate anions with the BH adducts BH ⋅S(CH ) or BH ⋅THF. The highly-energetic, nitro-, trinitromethyl-, and fluorodinitromethyl- substituted triazolyl- and tetrazolyl-trihydridoborate anions were synthesized in this manner and characterized by vibrational and multinuclear NMR spectroscopy and their crystal structures. The use of excess BH resulted in some cases in the addition of a second BH molecule bound more-weakly to one of the nitrogen atoms of the azole ring. All monoazolyl-trihydridoborates were thermally less stable than the parent azolate anions. A decomposition product of tetraphenylphosphonium (5-(trinitromethyl)-5H-2λ -tetrazol-2-yl)trihydridoborate, the tetraphenyl-phosphonium (dinitro-1H-tetrazol-5-yl)methanide monohydrate, was also structurally characterized, providing some insight into the decomposition pathways of the nitromethyl-substituted azolyltrihydridoborate anions.

The arsenic(III) and antimony(III) cyanides M(CN)3 (M=As, Sb) have been prepared in quantitative yields from the corresponding trifluorides through fluoride-cyanide exchange with Me3 SiCN in acetonitrile. When the reaction was carried out in the presence of one equivalent of 2,2'-bipyridine, the adducts [M(CN)3 ⋅(2,2'-bipy)] were obtained. The crystal structures of As(CN)3 , [As(CN)3 ⋅(2,2'-bipy)] and [Sb(CN)3 ⋅(2,2'-bipy)] were determined and are surprisingly different. As(CN)3 possesses a polymeric three-dimensional structure, [As(CN)3 ⋅(2,2'-bipy)] exhibits a two-dimensional sheet structure, and [Sb(CN)3 ⋅(2,2'-bipy)] has a chain structure, and none of the structures resembles those found for the corresponding arsenic and antimony triazides.

What was the inspiration for this cover design?When we received the invitation to submit ac over art, we immediately thought about the web comic "Cyanide &H appiness," written and illustrated by Rob Denbleyker,K ris Wilson, Dave McElfatrick, and Matt Melvin, and published on explosm.net. We are big fans of the often dark and surrealistic comics and wanted to incorporate it into the cover art. Luckily,t he people from C&H were okay with us using some of their characters. The inspiration behind the cyanide work in general is actually going back several years. My group was and still is heavily involved in the synthesis of metal polyazides. Afew years ago, we published the synthesis of binary Group 13 azides in Angewandte Chemie. Azide and cyanide are both pseudohalides and we were wondering if the reaction chemistry of the Group 13 azides can be directly applied to the cyanides. While we were surprised that there is adistinct difference, we were also happy because this gave us an excuse to further look into this chemistry.What other topics are you working on at the moment?Besides our research on metal cyanides, we are active in the following areas:h igh energy density materials (HDEM), environmentally friendly,g reen energetic materials (GEMs), polynitrogen and high nitrogen compounds, chemistry at the limits of oxidation and coordination, the chemistry of superacidic systems, fluorine chemistry,a sw ell as the synthesis and characterization of novel carbocation and fluorocarbon compounds.Is your current researchm ainly curiosity driven (fundamental) or rather applied?Our work features ah ealthy mix of fundamental and applied research. Some topics such as the chemistry of superacidic systems or at the limits of oxidation and coordination are currently driven by curiosity,w hereas other topics such as the research on energetic materials are strongly applied.How did each team member/collaborator contribute to the work? Invited for the cover of this issuei st he group of Ralf Haiges at the University of Southern California.T he image depicts characters from the popular web comic "Cyanide &H appiness" alongside some of the cyanide complexes synthesized. Read the full textoft he article at