Reductive nitrosylation of Group VIIIb compounds

Gwost, D.; Caulton, Kenneth G.

doi:10.1021/ic50127a030

Cited by 68 publications

(43 citation statements)

References 3 publications

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“…All reactions were carried out under argon or nitrogen atmospheres in dry, degassed organic solvents. HNEt3[Fe(N0)2C12] and Fe(N0)2(PPh3)Cl were prepared using the method of Gwost and Caulton (4) The identity of the two thiourea complexes prepared using this technique was confirmed by EPR spectroscopy but no analytical data are available since the compounds could not be isolated as pure crystalline solids. Solutions of the remaining complexes in methanol or ethanol were prepared by adding excess anionic ligand to M FeC12 followed by the passage of NO gas for 5 min (2).…”

Section: Methodsmentioning

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: Methodsmentioning

confidence: 99%

“…The first successful isolation of one of these compounds occurred in 1973 when deep purple crystals of Fe(NO),-(PPh,)Cl were prepared by the reaction of triphenylphosphine with [Fe(NO),Cl,]- (4) (6) were synthesized from the diamagnetic cluster, [Fe,S,(NO),]-(2k). Only two other paramagnetic iron dinitrosyl compounds have been isolated.…”

Section: Introductionmentioning

confidence: 99%

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Bryar¹,

Eaton²

1992

Can. J. Chem.

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“…Complex 5 also undergoes a similar reactivity profile in THF but appears to form the {FeNO} 7 species more rapidly (6 h). The established reductive nitrosylation [75] reaction of HNO with ferric hemes is among the most sensitive chemical tests for HNOreleasing molecules where HNO provides both the electron and NO to form an {FeNO} 7 ferrous-NO heme [39,76,77]. Additionally, M(III)-porphyrin complexes have been demonstrated as efficient traps for HNO [76,78,79].…”

Section: {Feno} 8 Spectroscopic Propertiesmentioning

confidence: 99%

Synthesis, properties, and reactivity of a series of non-heme {FeNO}7/8 complexes: Implications for Fe-nitroxyl coordination

Sanders

Patra

Harrop

2013

Journal of Inorganic Biochemistry

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“…Four coordinate cationic species (I) supported by both nonchelating and chelating amine, phosphine, phosphite and alkene ligands have been synthesized and characterized [7]. Many have been the subject of single crystal X-ray diffraction investigations [8].…”

Section: Introductionmentioning

confidence: 99%

“…Many have been the subject of single crystal X-ray diffraction investigations [8]. A number of salts of the form I have been shown to exhibit conductivity [7], and the electrochemistry of [{(EtO) 3 P} 2 Co(NO) 2 ] [BF 4 ] has been studied [9]. In an example of applied reaction chemistry, [L 2 Co(NO) 2 ] þ X À (L ¼ MeCN, PhCN, Me 2 CO; L 2 ¼ COD, norbornadiene; X ¼ PF 6 , BF 4 , ClO 4 ) have been reported by Tkatchenko and co-workers to be pre-catalysts for the oligomerization of butadiene, norbornadiene, styrene, isoprene and phenylacetylene [10].…”

Section: Introductionmentioning

confidence: 99%

[(TMEDA)Co(NO)2][BPh4]: A versatile synthetic entry point to four and five coordinate {Co(NO)2}10 complexes

Crimmin

Rosebrugh

Tomson

et al. 2011

Journal of Organometallic Chemistry

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Reductive nitrosylation of Group VIIIb compounds

Cited by 68 publications

References 3 publications

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Electronic configuration and structure of paramagnetic iron dinitrosyl complexes

Synthesis, properties, and reactivity of a series of non-heme {FeNO}7/8 complexes: Implications for Fe-nitroxyl coordination

[(TMEDA)Co(NO)2][BPh4]: A versatile synthetic entry point to four and five coordinate {Co(NO)2}10 complexes

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