Ligand homoleptic complexes

Hahde ligands are found in homoleptic complexes as well as in mixed ligands systems. HaUde complexes of Ir(IV) such as [IrCy [16918-91-5] are readily reduced to Ir(III) species, eg [IrCy [14648-50-1], in neutral or basic solution, or in the presence of reducing agents such as KI, oxalate, or photochemical activation (173). 

Allyl Complexes. Allyl complexes of uranium are known and are usually stabilized by cyclopentadienyl ligands. AEyl complexes can be accessed via the interaction of a uranium halide and an allyl grignard reagent. This synthetic method was utilized to obtain a rare example of a "naked" homoleptic allyl complex, U(T -C2H )4 [12701 -96-17, which decomposes at 0°C. Other examples, which are more stable than the homoleptic allyl complex have been synthesized, ie, U(allyl)2(OR)2 (R = alkyl), U(allyl)2X (X = halide), and U(allyl)(bipy)2. 

In a similar fashion, the homoleptic complex [Pd(ITmt) ] lb readily reacts with O2 to form the corresponding peroxo-complex 2b (Scheme 10.1). This complex, npon exposure to CO, leads to the peroxo-carbonate complex 3b [10]. Under the same reaction conditions, the formation of 3a does not occur, presumably due to the larger steric hindrance of the Mes ligand. 

Homo- and heteroleptic complexes of Cd alone and of Cd and Hg with the ligand dicyanamide (dca) N(CN)2-, homologous to cyanamide NCN2-, have been studied in various solvents (formation constants of the complexes [M(dca) ](" 2> (M = Cd, Hg l < n < 4)), with the result that the complexes of Hg are more stable than those of Cd. Otherwise, obviously no studies on the isolated compounds M(dca)2 or on homoleptic complexes derived therefrom have been published. 

Homoleptic complexes have been obtained also with tetrakis(l-pyrazolyl)borates, e.g., [ B(pz)4 2Cd] and [ B(3-Mepz)4 2Cd] (both P2 jc, Z = 2) in both compounds structure analyses the ligands have been shown to coordinate trihapto, i.e., with one pz ring free. In both cases Cd has a distorted octahedral environment, with averaged structural data very similar to those for the tris(l-pyrazolylhydridoborate complexes.201 Variable-temperature 3H NMR studies of these and of mixed complexes with tris- and bis(l-pyrazolylhydridoborates indicate fluxional behavior (coalescence temperatures and barriers for the dynamic processes are given). 

Dichalcogenolene ligands form complexes with main group and d transition metal ions.103 Bis( 1,2-dithiolene) complexes have been obtained for metals, such as Cr, Mn, Ni, Cu, Zn, for the first row, Pd, Ag, and Cd for the second row, and Pt, Au, and Hg for the third row. Homoleptic /ra(l,2-dithiolcnc) complexes have been obtained for Ti, V, Cr, Zr, Nb, Mo, Tc, Ru, Ta, W, Re, and Os. Fe and Co have been found both in bis and /ra(l,2-dithiolene) complexes, although /ra(l,2-dithiolene) complexes containing these metal ions... 

Particularly interesting are the homoleptic complexes 46 to 49 (Figure 2.3-7) in which Ni or Pt atoms are tetrahedrally coordinated by four Ga-R or In-R ligands [71, 72]. These compounds are analogues of Ni(CO)4. They have relatively short M-Ga or M-In bond lengths, and quantum-chemical calculations verify an effective 71-back bonding of electron density from the transition metal atom into the empty p-orbitals of the E-R groups. 

Plummer, D.T. and Angelici, R.J. (1983) Synthesis and characterization of homoleptic complexes of the chelating bidentate isocyano ligand tert-BuDiNC. Inorg. Chem., 22, 4063. 

Manganese forms a large number of mononuclear complexes in oxidation states II, III, and IV with acyclic and other common ligands. The complexes primarily are six-coordinate species with octahedral or pseudo-octahedral geometries. Some exceptions to this categorization are the tetraoxo anions in oxidation states V, VI, and VII and the manganocenes. Table 1 contains electrochemical data for representative redox couples in which the Mn coordination environment remains invariant with oxidation state. Many entries are for homoleptic complexes, but some species with mixed... 

The trans influence is another common electronic effect observed in coordination complexes. It is perhaps best known in planar d8 species such as Pt(II) complexes and we have developed an LFMM treatment for a range of ligands (21). Since we use homoleptic complexes as the basis for parameterization and not all species are available experimentally, this study was based exclusively on DFT. 

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