A phosphorus-supported multisite coordination ligand containing three imidazolyl arms and its metalation behaviour. An unprecedented co-existence of mononuclear and macrocyclic dinuclear Zn(ii) complexes in the same unit cell of a crystalline lattice.
The reaction of (S)P[N(Me)NH(2)](3) with three equivalents of 4(5)-imidazolecarboxaldehyde afforded, in situ, (S)P[N(Me)N[double bond, length as m-dash]CHIm](3) (Im = imidazolyl). The reaction of the latter with metal salts afforded mononuclear complexes [{(S)P[N(Me)N[double bond, length as m-dash]CHIm](3).M}][X](2) [M = Co, X = NO(3); M = Ni, X = ClO(4); M = Cd, X = NO(3)]. In these compounds, in the cationic part, the metal ion is bound by three imino and three imidazolyl nitrogen atoms to generate a trigonal prismatic type of coordination environment. Structural analysis of the zinc complex showed the presence of a mononuclear [{(S)P[N(Me)N[double bond, length as m-dash]CHIm](3).Zn}][NO(3)](2) and a dinuclear 20-membered metallamacrocycle [{(S)P[N(Me)N[double bond, length as m-dash]CHIm](3).Zn}(2)][NO(3)](4) in the same unit cell. Solution studies of the zinc complex revealed a monomer-macrocycle equilibrium.
Chandrasekhar
Vadapalli
V
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, India. vc@iitk.ac.in
Azhakar
Ramachandran
R
Pandian
Balasubramanian Murugesa
BM
Boomishankar
Ramamoorthy
R
Steiner
Alexander
A
D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry*; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010758:Phosphorus / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D017967:Zinc Compounds / Q000737:chemistry*
D007093:Imidazoles; D008024:Ligands; D047028:Macrocyclic Compounds; D017967:Zinc Compounds; D010758:Phosphorus; C029899:imidazole