Characterization of structurally unusual diiron N(x)H(y) complexes.
نویسندگان
چکیده
A series of fascinating diiron complexes featuring bridging N(x)H(y) ligands stabilized by tris(phosphine)borate ([PhB(CH(2)PR(2))(3)] = [PhBP(R)(3)]) ligands have been characterized. Hydrazine activation by [PhBP(R)(3)]Fe-Me (R = Ph or cyclohexylmethyl) leads to diiron Fe(2)(mu-eta(1):eta(1)-N(2)H(4))(mu-eta(2):eta(2)-N(2)H(2)) complexes featuring both bridging hydrazine and hydrazido ligands. Thermolysis of {[PhBP(CH(2))(Cy)(3)]Fe}(2)(mu-eta(1):eta(1)-N(2)H(4))(mu-eta(2):eta(2)-N(2)H(2)) at 22 degrees C leads to a structurally unusual {[PhBP(CH(2))(Cy)]Fe}(2)(mu-eta(1):eta(1)-N(2)H(2))(mu-NH(2))(2) complex featuring bridging HN horizontal lineNH and NH(2)(-) ligands. This contrasts with {[PhBP(Ph)(3)]Fe}(2)(mu-eta(1):eta(1)-N(2)H(4))(mu-eta(2):eta(2)-N(2)H(2)), which can be chemically oxidized to produce either {[PhBP(Ph)(3)]Fe}(2)(mu-eta(1):eta(1)-N(2)H(2))(mu-eta(2):eta(2)-N(2)H(2)) or {[PhBP(Ph)(3)]Fe}(2)(mu-NH)(2), depending on the conditions. The former product is the only known complex to contain bridging N(2)H(2) ligands in each of their limiting states of oxidation (HN horizontal lineNH vs HN-NH(2-)). The latter product constitutes the first example of a diiron Fe(2)(mu-NH)(2) diamond-shaped core.
منابع مشابه
Ab Initio Studies on the Interplay between Unconventional B•••X Halogen Bond and Lithium/Hydrogen/Halogen Bond in HB(CO)2•••XCN•••YF (X = Cl, Br; Y = Li, H, Cl) Complexes
In this paper, ab initio calculations were performed on the ternary complex formed by HB(CO)2, XCN (X = Cl, Br) and YF (Y = Li, H, Cl). In these complexes boron act as a non-classical electron donor to form a unconventional halogen bond. The cooperative effect between the B•••X halogen bond and lithium/hydrogen/halogen bond was investigated. The calculated results show that the B•••X and N•••Y ...
متن کامل(19)F NMR study of ligand dynamics in carboxylate-bridged diiron(II) complexes supported by a macrocyclic ligand.
A series of asymmetrically carboxylate-bridged diiron(ii) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar(4F-Ph)CO2)2] (10), [Fe2(F2PIM)(Ar(Tol)CO2)2] (11), and [Fe2(F2PIM)(Ar(4F-Ph)CO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT (19)F NMR spectroscopy. These complexes are part of a rare family of syn N-donor dii...
متن کاملSynthesis, Characterization and Antibacterial Properties of Some Thiocyanato Bridged Heteronuclear Complexes of Nickel
A series of heterobinuclear, thiocyanato-bridged complexes of cations [M(NH2X)6 ] 2+, and [M(en)3 ] 2+ (where X = H, Ph; M=Cu, Co, Cd, Zn) with anion [Ni(NCS)4 ] 2 –have been prepared by 1:1 molar ratio. The complexes have been characterized by FT-IR, 13C NMR and UV-vis spectroscopy, metal analysis, magnetic and conductance studies. The complexes have the following composition: [M(NH2 X)5 ][Ni(...
متن کاملModeling features of the non-heme diiron cores in O2-activating enzymes through the synthesis, characterization, and oxidation of 1,8-naphthyridine-based complexes.
Multidentate naphthyridine-based ligands were used to prepare a series of diiron(II) complexes. The compound [Fe(2)(BPMAN)(mu-O(2)CPh)(2)](OTf)(2) (1), where BPMAN = 2,7-bis[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine, exhibits two reversible oxidation waves with E(1/2) values at +310 and +733 mV vs Cp(2)Fe(+)/Cp(2)Fe, as revealed by cyclic voltammetry. Reaction with O(2) or H(2)O(2) aff...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 131 30 شماره
صفحات -
تاریخ انتشار 2009