Pentamethylendiazirine (N͡=N) has been found in metal carbonyl compounds as a monodentate two electron ligand (π-CH3C5Η4Mn(CO)2 N͡=N, (OC)5W N͡=N) or as a bidentate four electron ligand ((OC4M (N͡=N)2M(CO)4 (M = Mo, W), (OC)4Fe N͡=N Fe(CO)4). The reaction of Fe2(CO9 with diazirine affords the isocyanate and/or methylenamino-bridged complexes (OC)3Fe(NCO) (N=C< )Fe(CO)3 and (OC)3Fe (N=C< )2Fe(CO)3.
Dihydrido-iridium(III) complexes of the general formula IrH2(aa)(PPh3)2 (aa = L-alaninate, L-valinate, L-prolinate and L-phenylalaninate, 1 - 4 ) have been synthesized. Reactions of 1 - 3 with phenylacetylene give the hydrido-di(phenylethynyl) complex IrH(C≡CPh)2(PPh3)3 (5). The latter compound is also formed from IrH3(PPh3)3 and phenylacetylene. All complexes have been characterized by NMR (1H, 13C, 31P) and IR spectroscopy.
The reaction of bis(2,3,4,6-tetra-0-acetyl-β-D-glucopyranosyl)disulfide with (Ph3P)2Pt(C2H4) gives cis-di(2,3,4,6-tetra-0-acetyl-l-mercapto-β-D-glucopyranosid)bis(triphenylphosphane)platinum (II). A dithiocarbimato complex (Ph3P)2Pt(S2CNR) has been isolated from cis-(Ph3P)2PtCl2, CS2 and 1-0-Methyl-2-amino-2-deoxy-4,6-benzyliden-α,β-D-glucopyranoside. Metal complexes with metal-carbon bonds have been prepared by oxidative addition of monosaccharide halides to (Ph3P)2Pt(C2H4) or to cobalt(I) cobaloxime, respectively. From the reaction of (Ph3P)2Pt(C2H4) with 2,3,4,6 -Tetra-O-acetyl-α-D-glucopyranosyl-bromide the anomers trans-(α- and β-glucopyranosyl) Pt(PPh3)2Br have been obtained. This indicates a radical reaction.