Preparation and Characterization of Group 13 Cyanides

Abstract

Binary Group 13 cyanides [PPh ][Ga(CN) ], [PPh ] [In(CN) ], and [PPh ] [Tl(CN) ] were obtained in quantitative yields from the corresponding metal trifluorides MF (M=Ga, In, Tl) by fluoride-cyanide exchange reactions with Me SiCN in the presence of stoichiometric amounts of [PPh ]CN in acetonitrile solution. The 2,2'-bipyridine (bipy) adducts [(bipy) Ga(CN) ][Ga(CN) ], [(bipy)In(CN) ], and [(bipy)Tl(CN) ] were obtained from the reaction of MF with Me SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF with Me SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py) Ga(CN) ], [(py) In(CN) ], and [(py) Tl(CN) ]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X-ray crystal structures.

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

“…Contrary to our expectations, the absorption band of 2184 cm –1 , corresponding to the stretching vibrations of CN, had a low intensity, while the band of 436 cm –1 , corresponding to the highly symmetric oscillations of Ga–C, was of a high intensity. This is in good agreement with theoretical calculations made for the [Ga­(CN) 4 ] − anion . We believe that this effect is due to the T d symmetry of the anion and weak charge separation between atoms in the anion.…”

“…Compound 5 had a remarkable ionic structure formed by a trinuclear cation and a Ga­(CN) 4 anion (Figure ). The structural data on tetracyanogalates are rather limited: CCDC exhibits data on [Et 4 N]­[mesGa­(CN) 3 ], [PPh 4 ]­[Ga­(CN) 4 ], [(bipy) 2 Ga­(CN) 2 ]­[Ga­(CN) 4 ], and [Ga­(CN) 3 (py) 2 ], , while also a few related structures Li­[Ga­(CN) 4 ], Cu­[Ga­(CN) 4 ], Ga­(CN) 3 are not registered with CCDC. The geometry 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

“…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. , B3LYP calculations 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 . However, TZ2P+f CCSD­(T) quantum mechanical methods have reported that AlNC is 23 kJ/mol lower in energy than AlCN .…”

MCn (M = Ga, In, Tl) Coordination Polyhedra in Crystal Structures

“…The complex GaC 3 (δ = 0.054 Å) with the site symmetry C 3 occurs only in a single case and is in the GaC 27 H 33 structure {FAVWAA} [18] [22], GaMe 3 (t-Bu 2 Im) {FABYOZ} [23], Ca[GaMe 4 ] 2 (Ga(1) and Ga(2)) {BESREZ} [24], and InMe 3 (t-Bu 2 Im) {FABYUF} [23]. The studied set of selected structures includes a single structure, PPh 4 [Ga(CN) 4 ] {MEDBAB} [20], containing the GaC 4 CP with the positional symmetry S 4…”

“…have the positional symmetry C 1 . For indium and thallium each, there is a single example of the pentacoordinated state, namely, the isostructural (PPh 4 ) 2 [M(CN) 5 ], where M = In {MEDCEG} [20] and Tl {MEDCAC} [20]. The indium and thallium atoms in these structures form CP in the shape of trigonal bipyramids in which the bonds between the metal atoms and the equatorial or axial carbon atoms have different lengths: The hexacoordinated state in the set of selected structures exists in only one gallium complex.…”