Preparation and Characterization of Group 13 Cyanides

Abstract

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

Synthesis and ε-Caprolactone Polymerization Activity of Electron-Deficient Gallium and Aluminum Species Containing a Charged Redox-Active dpp-Bian Ligand

“…This is in good agreement with theoretical calculations made for the [Ga(CN) 4 ] − anion. 76 We believe that this effect is due to the T d symmetry of the anion and weak charge separation between atoms in the anion. A toluene solution of paramagnetic compound 5 revealed a resolved isotropic EPR spectrum.…”

“…h i b i t e d .structural data on tetracyanogalates are rather limited: CCDC exhibits data on [Et 4 N][mesGa(CN) 3 ],90 [PPh 4 ][Ga(CN) 4 ], [(bipy) 2 Ga(CN) 2 ][Ga(CN) 4 ],76 and [Ga(CN) 3 (py) 2 ],76,91 while also a few related structures Li[Ga(CN) 4 ], Cu[Ga-(CN) 4 ],92 Ga(CN) 393 are not registered with CCDC. Thegeometry of the tetrahedral solvate-separated [Ga(CN) 4 ] − ion with average C−N 1.154 Å and average Ga−C 1.919 Å interatomic distances were in excellent agreement with the parameters of the anion in [PPh 4 ][Ga(CN) 4 ] [C−N 1.145(2) Å; Ga−C 1.970(1) Å].…”

Reactions of Laser-Ablated Aluminum Atoms with Cyanogen: Matrix Infrared Spectra and Electronic Structure Calculations for Aluminum Isocyanides Al(NC)1,2,3 and Their Novel Dimers

“…11−14 Following the above halides, it could be expected that aluminum cyanides might be observed, since polymeric [Ga(CN) 3 ] has been prepared and characterized by X-ray powder diffraction and the [Ga(CN) 4 ] anion has been synthesized with the [PPh 4 ] counterion. 15,16 B3LYP calcu-lations have shown that donor−acceptor complexes between nitriles or isonitriles and Al, Ga, or In hydrides or chlorides react to form monomeric cyanides and larger ring species. 17 However, TZ2P+f CCSD(T) quantum mechanical methods have reported that AlNC is 23 kJ/mol lower in energy than AlCN.…”

Syntheses, Structures, and Infrared Spectra of the Hexa(cyanido) Complexes of Silicon, Germanium, and Tin

“…The EC 6 coordination skeletons of the investigated complexes adhere closely to the octahedral symmetry (Figures –) with only small deviations in the interligand angles of no more than 3.80(6) and 2.32(6)° from the ideal geometry of 90 and 180°, respectively, which is ascribed to the differences in the packing imposed by the crystal systems ( 1 , orthorhombic; 2 and 3 , monoclinic, Figure ). The cyanido ligands adopt the essentially linear end-on-C coordination (κ­(C)) mode that has been observed previously for other p -block complexes with coordination centers of groups 13 and 15. , Structure models tested during crystallographic structure refinement that feature isocyanido ligands E­(CN) x (NC) y 2– all were significantly inferior in predicting the diffraction data, leading to substantially increased disagreement factors ( R ).…”

“…In group 14, they take the form of EL 4 and EL 6 2– (E = Si–Pb, L = N 3 , NO 3 , NCO, NCS, NCSe). − However, there are only very few homoleptic cyanido complexes. This group of complexes is restricted to coordination centers of the less electronegative elements in groups 13 and 15 as P­(CN) 3 , Ga­(CN) 4 – , E­(CN) 5 2– (E = In, Tl, Sb, Bi) and Bi­(CN) 6 3– . − In group 14, the set of known complexes consist of the E­(CN) 4 type (E = Ge, Sn), for which, apart from in situ 119 Sn NMR spectral data for the Cl/CN ligand exchange to form Sn­(CN) 6 2– , little analytical data is available. − CN ligands possess a comparably low oxidation potential and this effects, for instance, the low thermal stability of P­(CN) 5 which readily eliminates cyanogen at ambient temperature to form P­(CN) 3 . The related P­(CN) 6 – complex, on the other hand, is thought to be stabilized by hypercoordination.…”