Amidino-complexes of Rhenium. Bidentate NN'- and ortho-Metallated Derivatives

DOI: 10.1039/DT9830002613

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2613 - 2624 (1983)

Update date:2022-09-26

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Authors:

Clark, J. Andrew

Kilner, Melvyn

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Article abstract of DOI:10.1039/DT9830002613

> complexes (I; R=Me or Ph; R'=Ph or C6H4Me-p), containing delocalised bidentate NN'-chelated amidino-groups, have been prepared by reactions of (i) <2> (X=Cl or Br) with R'N(Li)C(R)NR', (ii) X> with LiBuⁿ, (iii) with R'NHC(R)NR', and (iv) by decarbonylation of > complexes.Triphenylphosphine displaces CO from (I) to form > (II), which are more conveniently prepared by the reactions of (L'=PPh3 or AsPh3) with amidines in refluxing toluene.This reaction stops at the intermediate compound Br> when a NNN'-trisubstituted amidine is used.Related complexes Br> are formed when (II) are treated with hydrobromic acid. (X=Cl or Br) and <2> react with amidines to form o-metallated > (R=H, R'=Ph; R''=H; R=Me or Ph, R'=C6H4Me-p, R''=Me; R=Me or Ph, R'=Ph, R''=H) complexes which contain a six-membered o-metallated ring.Benzamidines (R=Ph) produce in addition an isomeric complex in which o-metallation of the R substituent occurs to give complexes having five-membered o-metallated rings.Intermediate 2X> complexes were isolated for R'=C6H4Me-p, R=Me, and X=Cl or Br.A 1,3-proton-shift mechanism for the o-metallation reaction is eliminated by the formation of the complex > (R'=C6H4Me-p) from R'N(Me)C(Me)NR'.Reaction schemes are suggested for the course of the reactions, and structures for the new complexes are proposed on the basis of spectroscopic data.

Full text of DOI:10.1039/DT9830002613

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