Ligands innocent ligand

Depending on the coordinative properties of the anion and on the degree of the cation s reactivity, the ionic liquid can be regarded as an innocent solvent, as a ligand (or ligand precursor), as a co-catalyst, or as the catalyst itself... 

Trigonal prismatic versus octahedral stereochemistry in complexes derived from innocent ligands. R. D. Wentworth, Coord. Chem. Rev., 1972, 9,171-187 (34). 

Electric polarizability, innocent ligands and spectroscopic oxidation states. C. K. Jorgensen, Struct. Bonding (Berlin), 1966,1, 234-248 (46). 

Jorgensen CK (1976) Deep-Lying Valence Orbitals and Problems of Degeneracy and Intensitites in Photo-Electron Spectra. 30 141-192 Jorgensen CK (1966) Electric Polarizability, Innocent Ligands and Spectroscopic Oxidation States. 1 234-248... 

Jorgensen, C.K. Electric Polarizability, Innocent Ligands and Spectroscopic Oxidation States. 

Lever ABP, Gorelesky SI (2004) Ruthenium Complexes of Non-Innocent Ligands Aspects of Charge Transfer Spectroscopy 107 77-114 LiB, see He J (2005) 119 89-119... 

The temperature dependence of the molar magnetic susceptibility (x) of an assembly of paramagnetic spins without interaction is characterized by the Curie behavior with x = C/T where C = /Vy2( 2.S (.S + l)/3k. It is a very common situation in the organometallic chemistry of radical species when the spin density is essentially localized on the metal atom. Since, in most cases, this atom is surrounded by various innocent ligands, intermolecular interactions are very weak and in most cases are reflected by a small contribution described by a Curie-Weiss behavior, with x = C/(T 0) where 0 is the Curie-Weiss temperature. A positive value for 0 reflects ferromagnetic interactions while a negative value — the most common situation — reflects an antiferromagnetic interaction. 

We finally point out that heteroleptic-dioxolene complexes with different redox non-innocent ligands can exhibit even further difficulty assignable redox changes.60... 

As briefly alluded to, there are different classes of redox-active ligands in addition to the above mentioned ones. For example, we have seen in Chapter 5, Section 8, that azo-groups (in particular, 2-(phenylazo)pyr-imidine) are able to undergo two separate one-electron reduction processes. Conjugated polynitriles (mnt, tcne, tcnq) also constitute an important class of redox-active molecules and the electrochemical behaviour of their metal complexes has been reviewed.107 The same holds as far as alkyldithiocarbamates (Rdtc) and their metal complexes are concerned,108 or nitrosyl complexes in their possible NO+[NO fNO redox sequence.109 Thus, we would like to conclude the present Chapter by discussing a few less known redox non-innocent ligands. 

Of particular interest are those complexes which serve as model compounds for biological systems such as the active center of the MoFe protein in nitrogenase.107 These complexes will be discussed in detail in the relevant chapters. It should be noted here, however, that WS2- is a non-innocent ligand, and thus complexes such as [Co(WS4)2]" (n = 2,3)108>109 and [Fe(WS4)2]" (n = 2, 3) can easily be prepared.110,111,112 In addition, some unusual complexes have been synthesized with WS2- as ligands. One such example is [Fe3W3S12]4 which contains the Fe3(/r3-S)2 center as depicted in Figure 11. 

---