Synthesis and Characterization of Six-Coordinate Nitrido Complexes of Vanadium(V), Chromium(V), and Manganese(V). Isolation of a Dinuclear, Mixed-Valent μ-Nitrido Chromium(III)/Chromium(V) Species
- 1 January 1996
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (4), 906-915
- https://doi.org/10.1021/ic9508031
Abstract
Photolysis of a series of octahedral monoazido complexes of the type [LM(III)(didentate ligand)(N(3))](n)(+)X(n) of vanadium(III), chromium(III), and manganese(III) in the solid state or in solution yields quantitatively the corresponding six-coordinate nitrido complexes [LM(V)(didentate ligand)(N)](n)(+)X(n) and 1 equiv of dinitrogen. L represents the macrocycle 1,4,7-triazacyclononane or its N-methylated derivative (L'), the didentate ligands are pentane-2,4-dionate (acac), 2,2,6,6-tetramethylheptane-3,5-dionate (tacac), picolinate (pic), phenanthroline (phen), and oxalate (ox), and X(-) represents perchlorate or hexafluorophosphate. The following nitrido complexes were prepared: [LV(V)(N)(acac)](ClO(4)) (6), [LCr(V)(N)(acac)](ClO(4)) (13), [LCr(V)(N)(tacac)](ClO(4)) (14), [LCr(V)(N)(pic)](ClO(4)) (15), [LCr(V)(N)(phen)](ClO(4))(2) (16), [LCr(V)(N)(ox)] (19), [L'Mn(V)(N)(acac)]PF(6) (21). Photolysis of [LCr(III)(N(3))(ox)] (17) in the solid state produces the &mgr;-nitrido-bridged mixed-valent species [L(2)Cr(2)(ox)(2)(&mgr;-N)](N(3)) (18). The structures of the precursor complex [L'Mn(acac)(N(3))]BPh(4) (20), of 13, and of [L'Mn(V)(N)(acac)]BPh(4) (21) have been determined by X-ray crystallography. Complex 13 crystallizes in the orthorhombic space group Pnma, with cell constants a = 27.187(5) Å, b = 9.228(2) Å, c = 7.070(1) Å, V = 1773.7(6) Å(3), and Z = 4; complex 20 crystallizes in the triclinic space group P&onemacr; with a = 14.769(5) Å, b = 16.83(1) Å, c = 16.96(1) Å, alpha = 108.19(5) degrees, beta = 105.06(4) degrees, gamma = 99.78(4) degrees, V = 3719(2) Å(3), and Z = 4; and complex 21 crystallizes in the monoclinic space group P2(1)/n with a = 10.443(3) Å, b = 16.035(4) Å, c = 21.463(5) Å, beta = 95.76(1) degrees, V = 3575.9(14) Å(3), and Z = 4. The Cr(V)&tbd1;N and Mn(V)&tbd1;N distances are short at 1.575(9) and 1.518(4) Å, respectively, and indicate a metal-to-nitrogen triple bond.Keywords
This publication has 24 references indexed in Scilit:
- Unusual solid-state reaction of [{CrL(acac)}2(µ-H3O2)][PF6]3. Isolation and crystal structures of [CrL(acac)F]PF6and [CrL(acac)(O2PF2)]PF6(L = 1,4,7-trimethyl-1,4,7-triazacyclononane, acac = pentane-2,4-dionate)J. Chem. Soc., Dalton Trans., 1994
- Spectroscopic studies of a square-pyramidal nitridochromium(V) complexJ. Chem. Soc., Dalton Trans., 1994
- An unusual species containing the mixed-valence [VIII(.mu.-N)VIV]4+ core obtained by reductive decomposition of Me3SiN3: [VBr2(N3)(dmpe)(.mu.-N)VBr(dmpe)2]Inorganic Chemistry, 1992
- Switching the mechanism of spin-exchange coupling in (.mu.-oxo)bis(.mu.-carboxylato)divanadium(III) complexes by protonation of the oxo bridgeInorganic Chemistry, 1991
- Photoirradiated and .gamma.-ray-irradiated reactions of manganese(III, IV, V) tetraphenylporphyrins in 2-methyltetrahydrofuran. Reactions of azidomanganese(III) porphyrinInorganic Chemistry, 1987
- Nitridokomplexe von Vanadium(V): [VNCl3] und VNCl2(Dipy)Zeitschrift für anorganische und allgemeine Chemie, 1986
- New triply hydroxo-bridged complexes of chromium(III), cobalt(III), and rhodium(III): crystal structure of tris(.mu.-hydroxo)bis[(1,4,7-trimethyl-1,4,7-triazacyclononane)chromium(III)] triiodide trihydrateInorganic Chemistry, 1982
- Ground-state electronic structure and the nature of excited states of oxotetrahalo complexes of chromium(V) and molybdenum(V): a self-consistent field multiple scattering X.alpha. studyInorganic Chemistry, 1980
- Neue μ‐Hydroxo‐Übergangsmetallkomplexe, I. Darstellung und Struktur des trans‐Diaqua‐di‐μ‐hydroxo‐bis[(1,4,7‐triazacyclononan)cobalt(III)]‐Kations; Kinetik und Mechanismus seiner BildungEuropean Journal of Inorganic Chemistry, 1979
- Preparation of Bis- and Tris(diamine)chromium(III) Complexes via Dimethyl Sulfoxide and Dimethylformamide Complexes. The Novel Series of cis-Bis(trimethylene-diamine)- and cis-Bis[(-)trans-1,2-cyclohexane-Diamine]chromium(III) Complexes.Acta Chemica Scandinavica, 1970