Crystal Structures of a Series of Complexes Produced by Reaction of Copper(I) Cyanide with Diamines

Abstract

A new synthetic procedure developed recently in our laboratories has made possible the synthesis of variety of new complexes of CuCN with diamines. Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. This procedure also provides an alternative pathway to a novel diamine complex reported by us previously, (CuCN)(3)(HMTA)(2) (1) (where HMTA = hexamethylenetetramine). The other diamine ligands used were 1,4-diazabicyclo[2.2.2]octane (dabco), 1,4-dimethylpiperazine (dmpip), piperazine (pip), 1,4-butanediamine (butda), N,N,N',N'-tetramethylethylenediamine (tetmen), and N-phenylpiperazine (phpip). Complex2, Cu(2)(CN)(3)(dabco-H), crystallizes in the hexagonal space group P6(3) with unit cell dimensions a = 8.174(3) Å, c = 8.083(4) Å, and Z = 2. Complex 3, (CuCN)(2)(dmpip), crystallizes in the monoclinic space group C2/m with unit cell dimensions a = 8.812(3) Å, b = 9.631(2) Å, c = 7.266(3) Å, beta = 113.40(3) degrees, and Z = 2. Complex 4, (CuCN)(2)(pip), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 9.439(3) Å, b = 10.561(2) Å, c = 8.870(3) Å, beta = 98.32(3) degrees, and Z = 4. Complex 5, Cu(2)(CN)(3)(pip-H), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 20.573(9) Å, b = 8.354(2) Å, c = 15.989(6) Å, beta = 133.70(3) degrees, and Z = 8. Complex 6, (CuCN)(2)(butda), crystallizes in the monoclinic space group P2(1)/c with unit cell dimensions a = 10.456(2) Å, b = 5.550(1) Å, c = 8.669(3) Å, beta = 106.80(2) degrees, and Z = 2. Complex 7, (CuCN)(2)(tetmen), crystallizes in the orthorhombic space group Cmc2(1) with unit cell dimensions a = 11.889(4) Å, b = 33.380(8) Å, c = 9.012(3) Å, and Z = 12. Complex 8, (CuCN)(phpip), crystallizes in the monoclinic space group P2(1)/cwith unit cell dimensions a = 17.8819(3) Å, b = 6.9190(1) Å, c = 8.6972(1) Å, beta = 96.720(1) degrees, and Z = 4.

Heterolytic Cleavage of the C−C Bond of Acetonitrile with Simple Monomeric CuII Complexes: Melding Old Copper Chemistry with New Reactivity

“…[3] Also, Cu I cyanide complexes are known to form large extended structures in the presence of amines. [4,5] Despite the reactivity of Cu II with CN À (to form [Cu I (CN) x ] xÀ1 complexes), simple Cu II salts in the presence of nitriles (alkyl cyanides) such as acetonitrile (CH 3 CN) are generally quite stable, and hence salts of the [Cu(CH 3 CN) 4 ] 2 ion are common Cu II starting materials for syntheses of other Cu II complexes. [1] The Cu I salts of CH 3 CN are also stable, and the use of [Cu(CH 3 CN) 4 ] salts in syntheses of Cu I complexes has been equally exploited.…”

“…[3] Also, Cu I cyanide complexes are known to form large extended structures in the presence of amines. [4,5] 4 ] salts in syntheses of Cu I complexes has been equally exploited. [1] In fact, metal-mediated splitting of the CÀCN bond in alkyl cyanides (e.g.…”

“…[1] In this regard, the recent finding that the intramolecular reaction of furans with alkynes can be catalyzed by AuCl 3 to afford phenols is of considerable interest. [3,4] The reaction was proposed to proceed by a [42] cycloaddition of the furan to the alkyne followed by cleavage of the resulting oxabicyclic adduct. [3] Although this mechanistic proposal is reasonable, the related intramolecular reaction of arenes with alkynes with catalysis by Pt II or Ru II [5] was proposed to take place by electrophilic aromatic substitution with an (h 2 -alkyne)metal electrophile.…”

Crystal structure of {μ4-[3,5-bis(4-pyridyl)-1,2,4-triazolate](μ2-cyanide)} dicopper(I), Cu2(C12H8N5)(CN), C13H8Cu2N6

“…In addition, the metal-triazolate frameworks exhibit special luminescent, magnetic, andfavorable gas-adsorption abilities [1,2]. On theother hand,copper cyanides have also been widely used as inorganic components owing to their structural diversity and interesting photochemical and photophysical properties [3,4]. However, only afew examples of Cu(I)-cyanide-triazolate systemswerereported [5,6].…”

3D-Interpenetrating Frameworks of 3∞[Cu2(CN)4(Me3Pb)2(bpy)] Containing the Rhombic [Cu2(µ3-CN)2] Motifs

“…The [Cu 2 (l 3 -CN) 2 ] motifs seem to display the essential role as the main building block in the structure of 1. It is worth mentioned that the number of the SCP containing the rhombic [Cu 2 (l 3 -CN) 2 ] motifs is now growing up [7,9,[18][19][20][21][22][23][24][25][26] presenting a rich collection of structural data on cyanide groups point towards the copper ions producing l 3 -CN units. The previously described 3D-framework of the coordination polymer [Cu 2 (CN) 2 (pip)] (pip = piprazine) even seems to involve l 4 -CN units, i.e.…”