Two copper(i)-nitro complexes [Tpm3-tBuCu(NO2)] (1) and [(Ph3P)2N][Tp3-tBuCu(NO2)] (2), containing steric bulky neutral tris(3-tert-butylpyrazolyl)methane and anionic hydrotris(3-tert-butylpyrazolyl)borate ligands, have been synthesized and characterized. Complex 2 adopts a unique κ2-binding mode of Tp3-tBu around the copper(i)-nitro environment in the solid state and shows a four-coordinated tetrahedral geometry surrounded by a nitro and three pz3-tBu groups in solution. Both complexes 1 and 2 allow for the stoichiometric reduction of NO2- to NO with H+ addition. The results of this effort show that increasing steric bulk and electron donation properties on the nitrogen ancillary ligand will improve the nitrite reduction ability of the copper(i)-nitro model complexes.

A series of fiveand six-membered-ring Al complexes bearing Schiff bases was synthesized and their application to the ring-opening polymerization of ε-caprolactone (CL) was studied. The five-membered-ring Al complexes have been shown to have a significantly higher polymerization rate than six-membered-ring Al complexes (2−3 fold for CL polymerization). The X-ray data revealed that the Al center of a five-membered-ring Al complex is farther from the Schiff base ligand than is that of a six-membered-ring Al complex. The results of density functional theory calculations also suggest that more space around the Al center of fivemembered-ring Al complexes may reduce the steric repulsion in CL polymerization and increase the catalytic activity of fivemembered-ring Al complexes.

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Boron mono- and di-cations featuring a nucleophilic N-heterocyclic olefin and the pentamethylcyclopentadienyl substituent have been prepared and structurally characterized. Experimental and theoretical investigations show that [η(5)-Cp*B-NHO](2+) is considerably more Lewis acidic than [η(5)-Cp*B-IMes](2+) due to the steric congestion imposed by the bent geometry of NHO around the central boron atom.

The β-diketiminato copper(II) L1CuCl−L4CuCl and their nitrite complexes L1Cu(O2N) and L2Cu(O2N) has been synthesized and characterized. The X-ray structure of the L1CuCl−L4CuCl complexes clearly indicates towards the mononuclear structure with...