Metal base interactions

Pickup, PG. 1999. Conjugated metallopolymers. Redox polymers with interacting metal based redox sites. / Mater Chem 9 1641-1653. 

Protonic initiation is also the end result of a large number of other initiating systems. Strong acids are generated in situ by a variety of different chemistries (6). These include initiation by carbenium ions, eg, trityl or diazonium salts (151) by an electric current in the presence of a quartenary ammonium salt (152) by halonium, triaryl sulfonium, and triaryl selenonium salts with uv irradiation (153—155) by mercuric perchlorate, nitrosyl hexafluorophosphate, or nitryl hexafluorophosphate (156) and by interaction of free radicals with certain metal salts (157). Reports of "new" initiating systems are often the result of such secondary reactions. Other reports suggest standard polymerization processes with perhaps novel anions. These latter include (Tf)4Al (158) heteropoly acids, eg, tungstophosphate anion (159,160) transition-metal-based systems, eg, Pt (161) or rare earths (162) and numerous systems based on tri flic acid (158,163—166). Coordination polymerization of THF may be in a different class (167). 

Group-IIIB halides ( 6.5.2), through interaction with neutral metal bases, lead to acid-base adducts in which the group-IIIB elements possess higher coordination numbers than before ( 6.5.2.1) ... 

This reaction is a principal method of forming IIIB-transition-metal cr bonds. The formation of thermodynamically favored alkali-metal halides or related salts and acids HX enhances the easy formation of those bonds. A second possible interaction between anionic metal bases and group-IIIB halides is a simple acid-base relationship without elimination of halide anions. However examples of this are rare, and they have been described often for group-IIIB compounds without halogen ligands ( 6.5.3.2). 

Group-IIIB element-transition-metal compounds have been synthesized by means of anionic metal bases and halide-free group-IIIB compounds. The carbonylate anions of Mn and Re interact with BHj to give [HjBMfCOlj]", which are best isolated as the tetraalkylammonium or phosphonium salts ... 

The appearance of a plasmon resonance is strictly related to a distinct size of the corresponding metal, based on the presence of a confined electron gas that interacts with light and so results in typical colours. Is there also a minimum size where plasmon resonance is no longer possible In any case this must happen if a particle reaches a typical molecular status. There are no longer freely mobile... 

When the metal complexes constitute the peripheral units (Fig. lb) and/or belong to the branches (Fig. 1 c) of a dendrimer, a number of equivalent metal-based centers are present since dendrimers are usually highly symmetric species by their own nature. The metal-based centers may or may not interact, depending on distance and nature of the connector units. Multielectron redox processes can therefore be observed, whose specific patterns are related to the degree of interaction among the various units. 

In dendrimers based on metals as branching centers (Fig. 1 d), the electrochemical behavior is even more complex since (i) each unit of the dendrimer is electro active, (ii) the chemical nature of the metal-based units constituting the dendrimer may be different, (iii) chemically equivalent units can be different from the topological viewpoint, and (iv) the degree of interaction among the moieties depends on their chemical nature and distance. 

Many observations concerning these trends had been made over the years, and in the 1950s S. Ahrland, J. J. Chatt, and M. Davies presented a classification of metals based on their preferred interaction with donor atoms. Class A metals are those that interact preferentially when the donor atom is in the first row of the periodic table. For example, they prefer to bond to N rather than P donor atoms. Class B metals are those which interact better when the donor atom is in the second row of the periodic table. For example, a class B metal would bond better to P than to N. The following table summarizes the behavior of metal atoms according to this classification. 

The broader subject of the interaction of stable carbenes with main-group compounds has recently been reviewed. Accordingly, the following discussion focuses on metallic elements of the s and p blocks. Dimeric NHC-alkali adducts have been characterized for lithium, sodium, and potassium. For imidazolin-2-ylidenes, alkoxy-bridged lithium dimer 20 and a lithium-cyclopentadienyl derivative 21 have been reported. For tetrahydropyrimid-2-ylidenes, amido-bridged dimers 22 have been characterized for lithium, sodium, and potassium. Since one of the synthetic approaches to stable NHCs involves the deprotonation of imidazolium cations with alkali metal bases, the interactions of alkali metal cations with NHCs are considered to be important for understanding the solution behavior of NHCs. 

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