134654-25-4Relevant academic research and scientific papers
Synthesis and characterization of the homoleptic aryloxides [M{O(2,4,6-t-Bu3C6H2)}2]2 (M = Mn, Fe), the adducts [Mn(OCPh3)2(py)2] and [Fe(OCPh3)2(THF)2], and the mixed complex [Fe{N(SiMe3)2}{μ-O(2,4,6-t-Bu3C 6H ...
Bartlett, Ruth A.,Ellison, Jeffrey J.,Power, Philip P.,Shoner, Steven C.
, p. 2888 - 2894 (2008/10/08)
Full title: Synthesis and characterization of the homoleptic aryloxides [M{O(2,4,6-t-Bu3C6H2)}2]2 (M = Mn, Fe), the adducts [Mn(OCPh3)2(py)2] and [Fe(OCPh3)2(THF)2], and the mixed complex [Fe{N(SiMe3)2}{μ-O(2,4,6-t-Bu3C 6H2)}]2: Evidence for primarily ionic M-O bonding. The characterization of several aryloxide and alkoxide derivatives of manganese and iron is reported. They were synthesized by treatment of the amides [M{N(SiMe3)2}2]2 (M = Mn, Fe) with the appropriate alcohol or phenol, in the presence or absence of donor molecules, to give the title compounds. Thus, the reaction of [M{N(SiMe3)2}2]2 (M = Mn, Fe) with 2 equiv of HOMes* (Mes* = 2,4,6-t-Bu3C6H2) gave [Mn(OMes*)2]2 (1) or [Fe(OMes*)2]2 (2). The intermediate species [Fe{N(SiMe3)2}(μ-OMes*)]2 (3) was isolated by using 1 equiv of HOMes*. The base adducts Mn(OCPh3)2(py)2 (4) (py = pyridine) and Fe(OCPh3)2(THF)2 (5) were isolated by treatment of the amide with 2 equiv of HOCPh3 in the presence of the base. The X-ray crystal structures of 1-3 show them to be dimers with aryloxide bridging. They were further characterized by IR spectroscopy. Variable-temperature 1H NMR spectroscopy shows that the bridging is quite strong and in the case of 2 is >15 kcal mol-1. The structures of 4 and 5 have very distorted 4-fold coordination at the metals. In all compounds the M-O bonding appears to be primarily ionic with little evidence for a strong M-O π interaction. Crystal data with Mo Kα (λ = 0.71069 A?) at 130 K: 1, a = 14.201 (6) A?, b = 28.677 (11) A?, c = 18.515 (8) A?, β = 103.30 (3)°, Z = 4, space group P21/c, 6851 data with I > 2σ(I), R = 0.07; 2, a = 14.343 (6) A?, b = 27.110 (9)°, c = 21.121 (8) A?, β = 101.51 (3)°, Z = 4, space group P21/c, 5035 data with I > 2.5σ(I), R = 0.77; 3, a = 10.194 (3) A?, b = 12.376 (6) A?, c = 12.558 (3) A?, α = 74.73 (3)°, β = 65.93 (2)°, γ = 84.61 (3)°, Z = 1 (dimer), space group P1, 5308 data with I > 2σ(I), R = 0.040; 4, a = 9.613 (3) A?, b = 10.614 (3) A?, c = 21.543 (5) A?, α = 79.88 (2)°, β = 78.70 (2)°, γ = 62.86 (2)°, Z = 2, space group P1, 4103 data with I > 2σ(I), R = 0.077; 5, a = 19.078 (4) A?, b = 9.562 (3) A?, c = 23.454 (3) A?, β = 119.06 (1)°. Z = 4, space group C2/c, 2936 data with I > 3σ(I), R = 0.039.
