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).