Carbenes structural properties

Although transition metal alkylidene complexes, i.e., carbene complexes containing only hydrogen or carbon-based substituents, were first recognized over 15 years ago, it is only relatively recently that Ru, Os, and Ir alkylidene complexes have been characterized. Neutral and cationic complexes of these Group 8 metals are known for both metal electron configurations d8 and d6. The synthesis, structural properties, and reactivity of these compounds are discussed in this section. 

Stable free carbenes derived from four- (13), six-, or seven-membered heterocycles 14 are also known. Carbenes of type 13 can possess a phosphorus [19] or a boron atom [69] within the heterocycle. These carbenes exhibit extreme values regarding their NMR spectroscopic ( carbene-c 285 and 312.6 ppm) and structural properties (angle N-Ccarbene-N 96.72(13) and 94.0(2)°). 

Carbene structures and properties can now be computed with chemical accuracy , despite the difficulties associated with multi-reference species such as singlet carbenes. This is particularly encouraging since the determination of singlet-triplet energy separations and accurate structures of carbenes, which very often are, at best, fleetingly observable intermediates, is extremely difficult experimentally. Transition structures also can be computed apparently with good accuracy and complement experimental studies of the reactions as well as the complex rearrangements commonly found in carbene chemistry. 

It should be clear by the definition given so far that the carbene-analogous state is limited to molecular species. The oligomer of EX2 (EX2)n is, of course, much more stable than EX2 in every respect. It should nevertheless be noted that also the oxidation number does not change in going from the monomer to the polymer the chemical, structural, and electronic properties of these species are completely different. 

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