AMINATION OF COMPLEXED CARBON-MONOXIDE BY N-NITROSAMINES - SYNTHESES AND STRUCTURES OF IRON CARBONYL AND NITROSYL COMPLEXES AND APPLICATIONS TO HETEROCYCLIC SYNTHESIS

Nitrosamines, R2NNO, undergo homolytic cleavage of the N-N bond on rea ction with iron carbonyls to give Fe(CO)2(NO)2 and organoiron products containing the ligands R2N, R2NCO, and R2NC, formally derived from am ination of complexed carbon monoxide, together with amines and ureas. The major products from dimethyl- and diethylnitrosamine are (OC)4-Fe( mu-CNR2)Fe(CO)2NO (4). The ethyl derivative has been crystallographica lly characterized: space group Pbca, a = 13.573(5) angstrom, b = 14.67 5(2) angstrom, c = 16.313(2) angstrom, V = 3249.3 angstrom3, Z = 8, R( F) = 0.057, and R(w) = 0.061 for 1152 reflections with I greater-than- or-equal-to 2sigma(I). These nitrosyls are thermolyzed to the bridging carbyne complexes (OC)3Fe(mu-CNR2)2Fe(CO)3 (9) and trinuclear [(OC)3F e]3-(mu3-CNR2)2 (21). Other products include (OC)3Fe[(mu-CNR2)(mu-OCNR 2)]Fe(CO)3 (5), (OC)3Fe]3-[(mu-NR2)(mu-OCNR2)]Fe(CO)3 (6), and (OC)3Fe [(mu-NR2)(mu-CNR2)]Fe(CO)3 (8). Thermolysis of the carbene complex(Me2 N)2CFe(CO)4 gives 5,8,9, and 21. The major product from N-methyl-N-nit rosoaniline and Fe2(CO)9 is the ortho-metalated ferracycle C6H4N(CH3)C OFe(CO)4 (7), which has been crystallographically characterized: space group P2(1)/c, a = 6.396(1) angstrom, b = 10.056(2) angstrom, c = 19. 025(3) angstrom, beta = 95.17(1)-degrees, V = 1218.7(1) angstrom3, Z = 4, RF = 0.032, and R(w) = 0.042 for 2008 reflections with I greater-t han-or-equal-to 3sigma(I). This ferracycle, tetracarbonyl(1-methyl-3-f erra-2-oxindole), undergoes trimethylamine N-oxide induced alkyne inse rtion to yield 3,4-disubstituted (Et-, MeO2C-) 1-methyl-2-quinolones, while photochemically induced insertion of an alkyne gives a product w here the 3,4-alkene bond has been reduced, together with the carbonyla tion product, N-methylisatin. One of two isomers Of (OC)3Fe[(mu-N(Me)P h)(mu-OCN(Me)Ph)]Fe(CO)3 has been structurally characterized with psi- anti-Ph and psi-anti-Me groups: P2(1)/n, a = 19.919(7) angstrom, b = 1 0.122(4) angstrom, c = 22.548(9) angstrom, beta = 98.90(3)-degrees, V = 4491(3) angstrom3, Z = 8, R(F) = 0.045, and R(w) = 0.062 for 4648 re flections with I greater-than-or-equal-to 3sigma(I). Thionitrites, RSN O, react with Fe2(CO)9 to give Fe(CO)2(NO)2 and Roussin's red esters [ (ON)2Fe(SR)]2, with Ni(CO)4 to give polymeric [RSNiNO]x, with Hg[CO(CO )4]2 to give CO(CO)3NO and unstable [CH3SCo(NO)2]2, with Mo-(CO)6 to g ive apolymeric product, with [C5H5Fe(CO)2]2 to give a mixture of [C5H5 Fe(CO)SMe]2 and [MeSFe(NO)2]2, and with [C5H5Mo(CO)3]2 to give C5H5Mo( CO)2NO. [PhSNiNO]x reacts with C5H5Na to give C5H5NiNO, while NO react s with [PhSNiC5H5]2 to give [PhSNiNO]x and C5H5NiNO. Fe(CO)2(NO)2 is s ynthesized by reacting ethyl nitrite with Fe2(CO)9 and from Fe(CO)4I2 and silver nitrite.