Transition-metal derivatives of arenediazonium ions. Part 8. The reactions of nitrosonium and arenediazonium ions with 2,2′-bipyridyl and 1,10-phenanthroline derivatives of Group 6 metal carbonyls

Abstract

The reaction between [W(CO)4(phen)](phen = 1,10-phenanthroline) and [NO][PF6] in methanol–toluene gives mer-[W(CO)3(phen)(NO)][PF6](1) whereas [Mo(CO)4(L–L)][L–L = bipy (2,2′-bipyridyl) or phen] reacts with either [NO]+ or [RN2]+(R = aryl) in acetone to produce fac-[M(CO)3(L–L)Z][BF4][Z = NO (2) or RN2(3)]. The complexes [Mo(CO)3(L–L)(PPh3)] and either [NO]+ or [RN2]+ in acetone give [M(CO)2(L–L)Z(PPh3)]+[Z = NO (4) or RN2(5)] which may also be prepared form (1)–(3) and PPh3. With an excess of PPh3, (2) or (3) yield [Mo(CO)Z(L–L)(PPh3)2]+[Z = NO (6) or RN2(7)], and with halide ion (1)–(5) afford [MX(CO)2(L–L)Z][X = Cl, Br, or I; Z = NO (8) or RN2(9)]. Iodine or Br2, reacts with (5) to give [{MoX3(L–L)(N2R)}n](10; X = I or Br). On refluxing (1) in acetone, rapid partial hydrolysis of he [PF6]– anion, and carbonyl substitution, gives [W(CO)2(phen)(NO)(O2PF2)](11).