Synthesis and structure of Fe(L'H)(NO)2, a tetracoordinate complex having a twelve-membered chelate ring, and its conversion to pentacoordinate FeL'(NO) through formal loss of "HNO" (L' = SCH2CH2NMeCH2CH2CH2NMeCH2CH2S-)

Baltusis, Laima; Karlin, Kenneth D.; Rabinowitz, H. N.; Dewan, John C.; Lippard, Stephen J.

doi:10.1021/ic50211a030

Cited by 72 publications

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“…X-ray structure determinations have been reported for only three of the six crystalline solids. The geometry of the Fe(NO), complex with the bidentate sulfur ligand was found to be pseudotetrahedral, with the angles showing only small deviations from the true tetrahedral values (7). The [Fe(NO),(SPh),]-anion was described to be a distorted tetrahedron, but the deviations from tetrahedral were larger than for the other sulfur complex (6).…”

Section: Introductionmentioning

confidence: 88%

“…Both of these have the stoichiometry Fe(NO),L where L is a bidentate ligand. In one case, the ligand is coordinated through sulfur atoms [-SCH2CH2NH-(CH3)CH2CH2CH2N(CH3)CH2CH2S-] (7), while in the other molecule, the 2-methyl-8-quinolinolate ion is coordinated through N and 0 (8). X-ray structure determinations have been reported for only three of the six crystalline solids.…”

Section: Introductionmentioning

confidence: 99%

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Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Bryar¹,

Eaton²

1992

Can. J. Chem.

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The electronic and geometric structures of paramagnetic iron dinitrosyl complexes have been investigated using electron spin resonance, infrared spectroscopy, and X-ray crystallography. It is concluded that these compounds are best described as 17 electron complexes with a d 9 configuration rather than the d 7 configuration assumed by most previous investigators. The anisotropy of the g values, determined from the electron spin resonance spectra of frozen solutions, varies considerably from complex to complex. The results are consistent with the supposition that all of the complexes have a distorted tetrahedral geometry, but the nature of the distortion changes as the ligands are varied. As a result of this variation there are changes in the nature of the spin-containing d orbital. Ligands containing hard, nonpolarizable donor atoms such as oxygen or fluorine produce a distortion towards a planar geometry, placing the odd electron in a predominantly d, 2-, 2 orbital, while those containing softer donor atoms such as phosphorus or sulfur give complexes with a different type of distortion, leading to placement of the odd electron in a predominantly dz2 orbital. Nitrogen and halide donor ligands produce smaller distortions, leading to spin-containing molecular orbitals with contributions from a mixture of d orbitals. In accordance with this model, the crystal structure of [Fe(NO),I,]-has been found to be only slightly distorted from regular tetrahedral coordination about the iron atom. TRACI R. BRYAR et DONALD R. EATON. Can. J. Chem. 70, 1917Chem. 70, (1992. Faisant appel 2 la resonance paramagnetique Clectronique (rpe), a la spectroscopie infrarouge et i la diffraction des rayons X, on a CtudiC les structures Clectroniques et geometriques des complexes paramagnetiques du dinitrosyl fer. On en conclut que la meilleure f a~o n de dCcrire ces composCs est de les considerer comme des complexes 2 17 klectrons possidant une configuration d 9 plut6t que la configuration d7 utilisee par la plupart des auteurs qui en ont trait6 anterieurement. L'anisotropie des valeurs g, determinee par les spectres rpe de solutions congelees, varie beaucoup d'un complexe 2 l'autre. Les resultats sont en accord avec l'hypothkse selon laquelle tous les complexes possedent une gkomktrie tCtraCdrique dCformCe, mais que la nature de la distorsion varie avec la nature des ligands. Un rksultat de cette variation amkne des changements dans la nature de l'orbitale contenant le spin. Les ligands contenant des atomes donneurs durs et non-polarisables, comme l'oxygkne ou le fluor, provoquent une distorsion vers une gComCtrie plane forqant 1'Clectron celibataire 2 1 occuper une orbitale principalement dX2-y2 alors que ceux qui contient des atomes donneurs plus mous, comme le phosphore ou le soufre, donnent des complexes~avec un type de distorsion different, conduisant . [Traduit par la rkdaction]

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Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Bryar¹,

Eaton²

1992

Can. J. Chem.

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“…88 The quantum yields of the reactions resulting in elimi nation of NO from Roussin's salt esters containing alkyl Later, a [1Fe-2S] dinitrosyl complex was prepared by the reaction of (FeL) 2 , where L is the N,N dimethyl N,N bis(2 mercaptoethyl)pro pane 1,3 diamine dianion, with NOPF 6 in dichloromethane. 99 Because of in vitro instabil ity, mononuclear iron dinitrosyl complexes are very difficult to crystallize, 24 The resulting complex is stable at -35 °C. Storage of the mononuclear iron complex in solution in air or an increase in the temperature as well as the presence of moisture lead to its decomposition.…”

Section: Methods For the Synthesis Of [Fe-s] Nitrosyl Complexesmentioning

confidence: 99%

Functional models of [Fe—S] nitrosyl proteins

Санина

Алдошин

2004

Russ Chem Bull

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“…Because of this interest in the biological activity of DNICs, several groups have been working to synthesize small-molecule analogues of these species [34][35][36][37][38][39][40]. The N 2 S 2 ligand, N,N 0 -bis(2-mercaptoethyl)-N,N 0 -diazacyclooctane (bme-daco), as well as an open-chain analogue originally synthesized in this laboratory [35], N,N 0 -dimethyl-N,N 0 -bis(2-mercaptoethyl)-1,3-propanediamine (L 0 H), have been employed as bidentate sulfur chelates to accommodate tetrahedral coordination of the Fe(NO) 2 group [36,37].…”

Section: Introductionmentioning

confidence: 99%

Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres

Harrop

Song

Lippard

2007

Journal of Inorganic Biochemistry

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Synthesis and structure of Fe(L'H)(NO)2, a tetracoordinate complex having a twelve-membered chelate ring, and its conversion to pentacoordinate FeL'(NO) through formal loss of "HNO" (L' = SCH2CH2NMeCH2CH2CH2NMeCH2CH2S-)

Cited by 72 publications

References 0 publications

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Functional models of [Fe—S] nitrosyl proteins

Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres

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