“…The length of the Fe(III)−O bond where the oxygen is situated trans to the apical tertiary nitrogen atom falls within the range of lengths previously determined for terminally bound methoxides in structurally characterized Fe(III) complexes (Table ) . However, the length of the Fe(III)−O bond where the oxygen is situated trans to the neutral basal benzimidazolyl nitrogen atom is longer than those previously determined for terminally bound methoxides, but is shorter than those for terminally bound methanols (Table ). − Although the Fe1−O2 bond length is marginally longer than that expected for a methoxide, based on a similar elongation of the basal bond length in cis -dichloro complex 1 , and the absence of any counterions, O2 was assigned as the oxygen atom of the methoxide. 1 ORTEP drawing (30%) of Fe III (H 2 ntb)(OMe) 2 , 2 .…”
By using the tripodal tetradentate ligand tris(2-benzimidazolylmethyl)amine (H(3)ntb), which can have several charge states depending on the number of secondary amine protons, mononuclear octahedral and dinuclear trigonal bipyramidal Fe(III) complexes were prepared. The reaction of mononuclear octahedral [Fe(III)(H(3)ntb)Cl(2)]ClO(4), 1, with 3 equiv of sec-butylamine in methanol led to the formation of mononuclear cis-dimethoxo octahedral Fe(III)(H(2)ntb)(OMe)(2), 2. One equivalent of the sec-butylamine was used to generate the monoanionic H(2)ntb(-) ligand where one of the three amines in the benzimidazolyl groups was deprotonated. The remaining 2 equiv were used to generate two methoxides that were coordinated to the octahedral Fe(III) ion in a cis fashion as demonstrated by the chlorides in 1. Reaction of 1 with excess (7 equiv) sec-butylamine generated the doubly deprotonated dianionic Hntb(2-) that stabilized the dinuclear mu-oxo Fe(III)(2)O(Hntb)(2), 3, adopting a five-coordinate trigonal bipyramidal geometry. The magnetic data for 3 are consistent with the antiferromagnetically coupled Fe(III) (S = 5/2) sites with the coupling constant J = -127 cm(-1).
“…The length of the Fe(III)−O bond where the oxygen is situated trans to the apical tertiary nitrogen atom falls within the range of lengths previously determined for terminally bound methoxides in structurally characterized Fe(III) complexes (Table ) . However, the length of the Fe(III)−O bond where the oxygen is situated trans to the neutral basal benzimidazolyl nitrogen atom is longer than those previously determined for terminally bound methoxides, but is shorter than those for terminally bound methanols (Table ). − Although the Fe1−O2 bond length is marginally longer than that expected for a methoxide, based on a similar elongation of the basal bond length in cis -dichloro complex 1 , and the absence of any counterions, O2 was assigned as the oxygen atom of the methoxide. 1 ORTEP drawing (30%) of Fe III (H 2 ntb)(OMe) 2 , 2 .…”
By using the tripodal tetradentate ligand tris(2-benzimidazolylmethyl)amine (H(3)ntb), which can have several charge states depending on the number of secondary amine protons, mononuclear octahedral and dinuclear trigonal bipyramidal Fe(III) complexes were prepared. The reaction of mononuclear octahedral [Fe(III)(H(3)ntb)Cl(2)]ClO(4), 1, with 3 equiv of sec-butylamine in methanol led to the formation of mononuclear cis-dimethoxo octahedral Fe(III)(H(2)ntb)(OMe)(2), 2. One equivalent of the sec-butylamine was used to generate the monoanionic H(2)ntb(-) ligand where one of the three amines in the benzimidazolyl groups was deprotonated. The remaining 2 equiv were used to generate two methoxides that were coordinated to the octahedral Fe(III) ion in a cis fashion as demonstrated by the chlorides in 1. Reaction of 1 with excess (7 equiv) sec-butylamine generated the doubly deprotonated dianionic Hntb(2-) that stabilized the dinuclear mu-oxo Fe(III)(2)O(Hntb)(2), 3, adopting a five-coordinate trigonal bipyramidal geometry. The magnetic data for 3 are consistent with the antiferromagnetically coupled Fe(III) (S = 5/2) sites with the coupling constant J = -127 cm(-1).
“…Four adjacent ethyl groups are on the same side, while the other four adjacent ethyl groups are on the opposite side. Such a conformation is the same as that in a recently synthesized Fe(OEP) compound 33 but differs from that in a Co(OEP) complex …”
The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP)(NO)(ONO), Ru(TPP)(NO)(OH), Ru(OEP)(NO)(ONO), and Ru(OEP)(NO)(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N(2)O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP)(NO)(ONO) (1): M = 789.79, space group I4/m (No. 87), a = 13.6529(6) Å, c = 9.7904(5) Å, V = 1825.0(2) Å(3), Z = 2, rho = 1.437 g cm(-)(3), purple bipyramid, 2theta(max) = 50.0 degrees, R(F) = 4.87% for 86 parameters and 838 reflections with I > 2sigma(I). Crystal data for Ru(TPP)(NO)(OH) (2): M = 760.79, space group I4/m (No. 87), a = 13.5423(4) Å, c = 9.7150(4) Å, V = 1781.7(1) Å(3), Z = 2, rho = 1.418 g cm(-)(3), dark red plate, 2theta(max) = 50.0 degrees, R(F) = 3.92% for 83 parameters and 811 reflections with I > 2sigma(I). Crystal data for Ru(OEP)(NO)(ONO).CH(2)Cl(2) (3): M = 794.77, space group P2(1) (No. 4), a = 10.7687(2) Å, b = 21.0320(2) Å, c = 8.5936(2) Å, beta = 102.683(1) degrees, V = 1898.85(6) Å(3), Z = 2, rho = 1.390 g cm(-)(3), black plate, 2theta(max) = 50.0 degrees, R(F) = 6.23% for 453 parameters and 4702 reflections with I > 2sigma(I). Crystal data for Ru(OEP)(NO)(OH).C(2)H(5)OH (4): M = 726.91, space group P2(1) (No. 4), a = 10.8474(7) Å, b = 21.002(1) Å, c = 8.3646(5) Å, beta = 103.571(1) degrees, V = 1852.4(2) Å(3), Z = 2, rho = 1.303 g cm(-)(3), brown plate, 2theta(max) = 45.0 degrees, R(F) = 6.74% for 421 parameters and 3527 reflections with I > 2sigma(I).
“…Many of these compounds are derived from or related to the title compound, (I) (Senge, 1996(Senge, , 2000a. Compound (I) is an archetypal high-spin iron±porphyrin and has served as a reference compound in several recent studies (e.g.…”
Key indicatorsSingle-crystal X-ray study T = 126 K Mean '(C±C) = 0.004 A Ê R factor = 0.048 wR factor = 0.137 Data-to-parameter ratio = 18.9For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
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