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NN'-Diarylacetamidines R'N HC( Me) N R', NN'-diarylbenzamidines R'N HC( Ph) N R' , and NN'-diarylformamidines R'NHC( H)NR' (R' = Ph or C6H4Me-p) react thermally or photolytically with [Re(CO),X] and/or [{Re(CO)4X},] (X = CI or Br) to afford air-stable, white complexes, [ Re(CO),{ R'NC( R) N H R'}X], containing monodentate amidine ligands. The corresponding lithioamidines (R = M e or Ph) gave white carbamoyl complexes [Re(CO),{CON(R')C(R)NR'}], which are converted thermally to NN'-bidentate [ Re(CO),{ R'NC( R) NR'}] and ortho-metallated [Re(CO),{R'NC(R)NHC6H3R"}{R'NC(R)NHR'}] (R" = H or Me). The latter complexes are also formed by further reaction of the carbamoyl complexes with the corresponding amidine. The carbamoyl complexes react with PPh3 to form [Re(C0)3(PPh3){ R'NC(R)NR'}]. Lithioamidines in excess react with [Re(CO),X] (X = CI or Br) complexes to give adducts formulated as Li+[Re(CO),{CON(R')C( R)NR'},] -. The new complexes are characterised, and structural data obtained by i.r. and n.m.r. spectroscopy. F -----1 * Calculated values in parentheses.

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