Nitrosyl derivatives of the unsaturated dihydrides [Mn-2(mu-H)(2)(CO)(6)(mu-L-2)] (L-2 = Ph2PCH2PPh2, (EtO)(2)POP(OEt)(2))

作者：Garcia M Esther; Melon Sonia; Ruiz Miguel A^*; Marchio Luciano; Tiripicchio Antonio

来源：Journal of Organometallic Chemistry, 2011, 696(2): 559-567.

DOI：10.1016/j.jorganchem.2010.09.079

• Manganese
• Metal-metal interactions
• Hydride ligands
• Nitrosyl ligands
• Carbonyl ligands
• Diphosphine ligands

The title dimanganese complexes react with NO (5% in N-2) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn-2(NO)(6)(mu-L-2)] in moderate yields, and they react rapidly with NO2 to give the corresponding hydride derivatives [Mn-2(mu-H)(mu-NO2)(CO)(6)(mu-L-2)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO2 to give first the nitro derivative (PPN)[Mn-2(mu-H)(H)(NO2) (CO)(6)(mu-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn-2(mu-CO)(CO)(5)(NO)(mu-dppm)] at room temperature or above (dppm = Ph2PCH2PPh2; PPN+ = [N(PPh3)(2)](+)). The latter anion reacts with (NH4)PF6 to give the hydride-bridged nitrosyl complex [Mn-2(mu-H)(mu-NO)(CO)(6)(mu-dppm)] and with [AuCl (PPh3)] to give the trinuclear cluster [AuMn2(mu-NO)(CO)(6)(mu-dppm)(PPh3)] (Mn-Au = ca. 2.68 angstrom; Mn-Mn = 2.879(2) angstrom). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF3SO3Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn-2(mu-NOMe)(CO)(6)(mu-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF4 center dot OEt2 to the nitrosyl-bridged hydrides [Mn-2(mu-H)(mu-NO)(CO)n(mu-dppm)(m)] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn-2(mu-H)(mu-NOH)(CO)(n)(mu-dppm)(m)]BF4, which were also thermally unstable and could not be isolated nor fully characterized.

• 出版日期2011-1-15