Abstract
Treatment of a THF solution of trans-[ReCl(N 2)L 4] (L PMePh 2) with a cyanamide, NCNR 2 (R Me, Et or H) or with cyanoguanidine, NCNC(NH 2) 2 , yields mer-[ReCl(N 2)(NCNR 2)L 3] ( 1) or mer-[Re(N 2)[Re(N 2){NCNC(NH 2) 2} 2L 3]Cl ( 2), respectively, which, to our knowledge, are the first mixed dinitrogen-cyanamide-type complexes to be reported. The former products ( 1, RMe or Et) can also be obtained from reaction of the benzoyldiazenido complex [ReCl 2(NNCOPh)L 3] with NCNR 2 in refluxing methanol; the Re(II) complex mer-[ReCl 2(NCNEt 2)L 3] ( 3) is also formed (conceivably via an unusual homolysis of the CN bond of the benzoyldiazenido ligand) and its crystal structure is reported. It shows an unusual pyramidal conformation at the amine N atom of the diethylcyanamide ligand which also exhibits a significant structural trans influence on the phosphine, behaving as a stronger net electron donor than the latter ligand.
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