An integrated laboratory experiment applying concepts and techniques developed in organic chemistry, inorganic chemistry, and instrumental analysis is presented for use by students interested in undergraduate research. The experiment incorporates some advanced laboratory practices such as multistep organic synthesis and purification, detailed reaction mechanism, air-sensitive metalation techniques, variable-temperature NMR experiments, cyclic voltammetry, and single crystal X-ray crystallography. Subsequently, students are presented with an experience that mirrors fundamental inorganic chemistry research practices found in laboratories throughout the world.

The synthesis, characterization, and catalytic activity of bis(2-pyridylmethyl)amine (BPMA) copper complexes incorporating olefinic pendent arms are reported. Four copper(I) and four copper(II) complexes were synthesised employing four different counterions [chloride (Cl-), perchlorate (ClO4-), trifluoromethanesulfonate (CF3SO3-), and tetraphenylborate (BPh4-)]. The counterions used ranged from coordinating (Cl-) to non-coordinating (BPh4-), producing different coordination modes in respective complexes. Solid state results obtained for the copper(I) complex incorporating the non-coordinating (BPh4-) counterion displayed an associative bond between the metal center and the C=C group in the olefinic arm of a neighbouring complex. This interaction led to augmentation of the C=C bond due to back-bonding from the metal center. Five solid state structures were obtained for the copper(II) complexes with two also displaying intermolecular associative bonding between olefinic pendent arms and the metal center. X-ray crystallography studies showed that the olefinic arm motifs incorporated were hemilabile. Solution studies indicated that the copper complexes had some inherent reducing power and could be potential candidates for use as catalysts in atom transfer radical processes. However, only moderate conversions and yields were obtained in atom transfer radical addition (ATRA) reaction studies performed utilizing the copper complexes due to the presence of a competing reaction.

The structures of five compounds consisting of (prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine complexed with copper in both the Cu(I) and Cu(II) oxidation states are presented, namely chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(I) 0.18-hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena-poly[[copper(I)-μ2-(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(5)N,N',N'':C(2),C(3)] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di-μ-chlorido-bis({(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)N,N',N''}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu(I) complexes results in either a discrete molecular species, as in (1), or a one-dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu(I) atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one-dimensional chain parallel to the crystallographic b axis. Three complexes with Cu(II) show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis-μ-chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core-bridged Cu2Cl2 moiety.

The complex [tris­(pyridin-2-ylmeth­yl)amine]­copper(II) bromide adopts a trigonal–bipyramidal coordination geometry about the CuII ion. The outer sphere bromine counter-ions are severely disordered.

In the crystal, weak Cu⋯Cl inter­actions between symmetry-related mol­ecules create a dimerization with a chloride occupying the apical position of the square-pyramidal geometry typical of many copper(II) chloride hetero-scorpionate complexes.