Organometallic Intramolecular-Coordination Compounds

I. Omae, Organometallic Intramolecular Coordination Compounds, Elsevier, Amsterdam, 1986. 

Organometallic intramolecular-coordination compounds containing a nitrogen donor ligand. 

Organometallic intramolecular coordination compounds containing a phosphorus donor ligand. I. Omae, Coord. Chem. Rev., 1980, 32, 235-271 (168). 

Omae Iwao. Organometallic intramolecular- coordination compounds. Amsterdam. Elsevier, 1986. 402 p. 

Dithiolene Complexes of Transition Metals 1660 Organometallic Intramolecular-Coordination Compounds. Recent Aspects in the 1661... 

Omae I (1986) Organometallic intramolecular-coordination compounds. Elsevier, Amsterdam (and references cited therein)... 

Organometallic Intramolecular-coordination Compounds, i.Omae, Elsevier Science Publishers Amsterdam and New York. 1986. 

Omae, I. Organometallic Intramolecular-coordination Compounds Elsevier Amsterdam, 1986. 

The second item for discussion concerns organometallic intramolecular-coordination compounds. These compounds have two types of bonds a -coordination bond in which the intramolecular-coordination bond is an unsaturated -coordination bond and a o-coordination bond formed by lone electron pair of a hetero atom to a metal atom. The former compounds are -coordination compounds, and the latter are o-coordination compounds. In these two types of compounds, an overwhelming majority of the latter organometallic intramolecular-coordination five-membered ring compounds are synthesized by cyclometalation reactions, because the latter products are very easily prepared regioselectively. The author has compiled many articles and published many reviews [41-55, 91, 96-99] and three monographs [56, 100, 101] concerning them since 1972. 

This research field is generally referred to as Cyclometalation Reactions, although the author had already reported Organometallic Intramolecular-Coordination Compounds Containing Carbonyl Groups in 1972 [41],... 

Thus, the author first reported the verification of intramolecular-coordination bonds in organometallic intramolecular-coordination compounds in the Japanese journal Kogyo Kagaku Zasshi, Vol. 69, April 1966 issue [5], including the transition metal compounds, as described in Chap. 3, and the verification with X-ray diffraction studies on these two diastereoisomers in 1968 [9] and 1969 [10], respectively. 

The first set of articles on the main group of metal organometallic intramolecular-coordination compounds is considered to be the series of articles on organoalumi-num compounds published by Bahr and Muller [1-3]. Since the IR and NMR spectra were not yet known in those days, however, no verification of intramolecular-coordination bonds in the product compounds was conducted utilizing these spectral data. They therefore showed data for the elementary analysis, molecular weight, and decomposition compounds of the products and two reaction routes for synthesis of the final product hence, they only guessed at the structures of intramolecular products described above. 

With regard to transition metal compounds, on the other hand, a report on the reaction of azobenzene with a dipentadienyl nickel compound by Kleiman and Dubeck [4] in 1963 is generally considered to be the first on organometallic intramolecular-coordination compounds, as shown in Eq. (3.1). 

Organometallic intramolecular-coordination compounds are defined schematically as shown in compound 4.4 in Fig. 4.2 [1]. 

The classifications of the organometallic intramolecular-coordination compounds shown in Fig. 4.6 have been reported in a monograph published in 1986 [1]. 

Fig. 4.4 Examples of organometallic intramolecular-coordination compounds containing a coordinating group, such as a Jt-vinyl, Jt-ally, cyclopentadienyl, or the aryl group...

As a consequence, these carbene atoms may be considered as coordinating atoms. Hence, the carbene compounds of Group 14 elements may be added to the coordinating atoms in the classification of organometallic intramolecular-coordination compounds in Fig. 4.8. 

---