
This chapter is a collection of the syntheses of ten different classes of group compounds. The first is the synthesis of gold(I) and gold(II) amidinate complexes. Next syntheses covers nickel(I) and (II)-iron tholate species of relevance to the metal sites in nickel–iron hydrogenases. The third syntheses involve dimethyl sulfoxide complexes of ruthenium(II). The fourth synthesis describes the isolation of two Cr(III) acetonitrile complexes. The fifth synthesis describes the synthesis of the complex (1R,2R-diaminocyclohexane)oxalatoplatinum(II), or oxaliplatin. Remaining with the group 10 metals, the next synthesis is that of tris(-dibenzylideneacetone)dipalladium. The seventh set of syntheses is unique because no metal derivatives are featured. The synthesis of the three-coordinate titanium(III) amido complex Ti{N(Bu t ) C6H3-3,5-Me2}3 by a straightforward procedure is also described. The next synthesis describes the synthesis of the deceptively simple complex TaCl4(TMEDA). The last synthesis describes the synthesis of the ligand 1,3,5-tri-tert-butyl cyclopenta-1,3-diene by two methods and conversion to its sodium and magnesium transfer reagents.
Homoleptic complexes in which alkyl or aryl groups are η1-bound to a transition metal form one of the cornerstones of organometallic chemistry. For example, most transition metals form both neutral and anionic complexes with σ-bonding aryl ligands. This chapter discusses the synthesis of the dimesityl iron (II) dimer (FeMes2)2 and its pyridine complex. It describes a series of homoleptic aryl complexes of the first row transition elements manganese, iron, and cobalt. The chapter features the transition metal elements iron and cobalt coordinated to naphthalene or anthracene in an η4 fashion. This coordination mode is indicative of weakened metal ligand bonding. Complexes with naphthalene or anthracene bonded in this way are of interest primarily because of their utility as synthons. It has been recently shown that sterically demanding m-terphenyl ligands can stabilize two-coordinate transition metal centers, in homoleptic complexes.
This chapter features the preparation of group 13–15 complexes of the organo-substituted group 13 metals aluminum, gallium, and indium, as well as different routes to the organoaluminum species {Al(η5-C5Me5)}4. Phosphido (R2P-) and arsenido (R2As-) derivatives of the heavier group 13 elements aluminum, gallium, and indium have been of interest for their potential as precursors to semiconductors such as gallium arsenide (GaAs) and indium phosphide (InP). The chapter describes the syntheses of aluminum(I) organo derivative pentamethylcyclopentadienyl aluminum(I), {Al(η5-C5Me5)}4. The ammonia complex of tri-tert-butylgallane is a colorless crystalline solid with a melting point of 42–46 °C. The (AlCp*)4 tetramer is obtained by reacting freshly prepared (Cp*AlCl2)2 with a small excess of potassium in toluene under reflux. The chapter concludes with the synthesis of tris(pentafluorophenyl)aluminum as its toluene adduct. This was effected in a simple manner via the reaction of trimethylaluminum with commercially-available B(C6F5)3.