Tricyanomethanide

Tetracyanome thane [24331-09-7] methanetetracarbonitdle, is prepared by heating silver tricyanomethanide [36603-81 -3] n.]ic id cyanogen chloride (42). 

A similar complex 80 is also produced in a reaction of cobalt(ll) nitrate with potassium tricyanomethanide (Ktcm) and benzotriazole (BtH). According to the X-ray data for this complex, the CoN6 octahedron is only slightly distorted, having the N-Co-N angles in the range of 88.37-91.16°. The equatorial Co-N(tcm) distances (2.106 and 2.110 A) are... 

Fig. 4 Comparison of Raman, IR, and IETS spectra of the tricyanomethanide (TCM) ion. IETS taken from an Al-AlOx-CsTCM-Pb device. Figure drawn using data from [49]...

Hipps KW, Aplin AT (1985) The tricyanomethanide ion an infrared, Raman, and tunneling spectroscopy study including isotopic substitution. J Phys Chem 89 5459-5464... 

The net conveniently referred to as the rutile net consists of 6-connecting, essentially octahedral nodes, each connected to twice as many 3-connecting, essentially trigonal nodes - this is an example of a 3,6-connected net. The series of isostruc-tural binary metal-tcm compounds, [M(tcm)2] (tcm- is the tricyanomethanide... 

Hg2(acridine)2(C104)2 is known by X-ray examination.109 Cyano carbanions such as the tricyanomethanide anion, C(CN)J, the p-tricyanovinylphenyldicyanomethanide and some propionides, e.g. the 1,1,3,3-tetracyanopropionide, form complexes with the Hgj+ ion with N—Hg—Hg—N— bonds.110 Dianions such as 2-dicyanomethylene-l,l,3,3-tetra-... 

Mercury(II) tricyanomethanide, Hg C(CN)3 2 is an ionic compound which is cleaved by hydrolysis.263 The compound is decomposed by heat to yield a voluminous brown ash. Mercury(II) dicyanamide has been described and a polymeric structure is suggested (Figure... 

The IR spectra and structures of the free tricyanomethanide carbanion and its potassium ion pair have been studied by both spectroscopic experiment and DFT B3LYP force field computations.4 According to the computations, the conversion of the free tricyanomethanide carbanion into an ion pair results in essential changes in the lower-frequency vibration. The experimental geometry agrees with an ion-pair structure with K+ along the C-C=N axis. 

Group IV. C-Donor ligands. Treatment of salts of Pt (Pd, Rh, Ir) with 1-benzoyl -iminopyridinium (L) gives the complexes [PtCl(L - H)L] (see p. 398).103 Dicyano-methanide complexes of Pt (Pd, Rh, Ir) have been prepared, e.g. equation (38) (see p. 398) 101 Tricyanomethanide complexes of Pt have been synthesized by oxidative... 

Syntheses of At(l)-tricyanomethanide and At(l)-azide compounds (pseudohalogen compounds of astatine)... 

Also possibly involving Mn—C bonds is the compound72 of the tricyanomethanide ion Mn C(CN)3 2 (Me2N)3PO 2. This colourless compound is not isomorphous with the octahedral Ni11 species, but also probably has an octahedral polymeric structure with bridging anions. 

Ruthenium(II) Treatment of [Ru(NH3)5(OH2)]2+ or [Ru(NH3)5(acetone)]2+ with L or [RuCl(NH3)5]2+ with zinc amalgam in the presence of L yields [RuL(NH3)5]2+ (L = acetonitrile, benzonitrile,358 substituted benzonitrile,196 358 359 acrylonitrile,360 hydrogen cyanide,36,37 ethyl cyano-formate,361 dicyanamide, malononitrile, substituted malononitrile, tricyanomethanide,362 4-cyano-l-methylpyridinium196). Reaction of a hundred-fold excess of RCHO (R = Ph, Me) with [Ru(NH3)6]2+ under alkaline conditions yields [Ru(NH3)sNCR]2+.363-365 The likely mechanism of this reaction is given in Scheme 12. An alternative route to nitrile complexes is by reaction of [Ru(NH3)sOH2]2+ with aldoximes, e.g. RMeC=NOH, to afford [Ru(NH3 )5 (NCMe)]2 + and... 

Alkylation of Organic Halides with Potassium Tricyanomethanide. The preparation of 1,1,1 - tricy anobutene-3 is given as a typical example of the experimental procedures used in the reaction of organic halides with potassium tricyanomethanide. 

A mixture of 29.0 grams (0.225 mole) of potassium tricyanomethanide (24), 26.6 grams (0.32 mole) of allyl bromide, and 500 ml. of acetonitrile was refluxed with stirring tor 72 hours. The mixture was cooled and Altered to give 21.8 grams (83.5%) of precipitated potassium bromide. The filtrate was concentrated and diluted with ether to precipitate the residual potassium salts. After filtering, the filtrate was concentrated and distilled to give 16.7 ml. (57.8%) of colorless liquid, b.p. 95° C./26 mm. 

The microcrystalline CT salts between cations 8 and 9 and the anions 1,1,3,3-tetracyanopropenide and tricyanomethanide showed a single broad ESR absorption band. The CT salts showed a photocurrent about 10 times larger than the darR current on irradiation at the CT absorption band. The ESR signal, which seems to originate from the charge carriers in the darR conduction, was slightly enhanced on the CT and near IR excitations (74BCJ448). 

TCNE is one among several compounds belonging to the class of poly- or percyanated olefinic acceptors. Indeed, CT complexes of [FeCpf] with, e.g., penta-cyanopropenide ([C3(CN)5] ) [28], hexacyanobutadienide ([C4(CN)g] ) [29], hexa-cyanotrimethylenecyclopropanide ([C3(C(CN)2 3] ) [30], as well as with the simplest representative tricyanomethanide ([C(CN)3] ) [36] have been reported. The respective 1 1 CT complexes with [FeCp ] have been structurally characterized and their magnetic properties studied. 

Tricyanomethanide ion. The very small deviations from planarity of this ion observed in certain salts have been attributed to crystal interactions. This ion can form interesting polymeric structures with metal ions. In the argentous compound the group acts as a 3-connected unit in layers based on the simplest 3-connected plane net, and these layers occur as interwoven pairs as described on p. 90. 

The unique structure adopted by silver tricyanomethanide, Ag[C(CN)3]is illustrated in Chapter 3 (p. 90). It consists of pairs of interwoven hexagonal layers in which Ag is approximately 0-5 A out of the plane of its three N neighbours. Presumably single plane layers would have too open a structure—compare KCu2(CN)3. H2O, in which there are K ions and H2O molecules to occupy the large holes in the sheets. 

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