Fe Hg Research Articles

The insertion of the [M(CO) 3(NN)] fragments (M = Mo, W; NN = 2,2′-bipyridine; 1,10-phenanthroline; ethylenediamine) into the HgX (X = Cl, Br, I, N 3, SCN) bonds of the [η 5-C 5H 5Fe(CO) 2(HgX)] complexes. Heterotrimetallic compounds with FeHgMX bondings

The tricarbonyl complexes [M(CO) 3(NN)(CH 3CN)] (M = Mo, W; NN = bipy, phen, en) react with the binuclear complexes [η 5-C 5H 5Fe(CO) 2(HgX)] (X = Cl,Br,I,SCN, N 3) to generate trinuclear products of the formula [η 5-C 5H 5Fe(CO) 2HgM(CO) 3(NN)X]. These complexes were characterized using IR and electronic spectroscopy. The results are interpreted as the insertion of M(CO) 3(NN) fragments into the HgX bonds to give the FeHgMX arrays, with the metallic centre, M, being seven-coordinate. The general properties of the new compounds and their reactivity towards monodentate bases and mercury halide derivatives are discussed.

Synthesis and solid-state structural characterization of bis (thiocyanatemercury)tetracarbonyliron

The bis (thiocyanatemercury)tetracarbonyliron, [Fe(CO) 4(HgSCN) 2], was prepared from [Fe(CO) 5] and Hg(SCN) 2, and studied by IR spectroscopy and X-ray diffraction. The compound crystallizes in the tetragonal space group I4, 1/ a. The unit cell, with dimensions of a = 13.778(3), c = 13.234(3) Å, V = 2512.3(9) Å 3, contains four molecules. The iron atom is octahedrally coordinated by four carbonyl groups and two mercury atoms in cis positions. The coordination of the mercury atoms is distorted square-planar, since, besides mercury-iron and mercury—sulphur bonds, there are also mercury—mercury and mercury-nitrogen interactions. The FeHg distance is 2.506(5)Å and the HgFeHg angle is 78.0(1)°.

Evidence of ironmercury bonds in complexes of ferrocene with mercuric chloride from mössbauer spectroscopy

Novel Mössbauer spectra of ferrocene/mercuric chloride adducts are reported, displaying anomalously high quadrupole splittings, which are interpreted as strong evidence for FeHg bonding. The results are discussed in conjunction with tilting of the cyclopentadienyl rings.

ChemInform Abstract: CRYSTAL STRUCTURE OF TETRAPHENYLARSONIUM CIS‐TETRACARBONYL(CHLOROMERCURIO)(DICHLOROMERCURIO)FERRATE

The crystal structure of the title compound has been determined by X-ray diffraction (heavy-atom) methods and refined by least squares to R 0.059 for 2 917 observed reflections. Crystals are triclinic P, a = 11.848(3), b= 13.524(4), c= 11.624(3)A, α= 123.87(2), β= 94.01 (2), γ= 90.91 (2)°, Z= 2. Within the anion, the two mercury atoms are bonded cis in the co-ordination sphere of the six-co-ordinate iron atom [Fe–Hg 2.560(3) and 2.516(4)A, Hg–Fe–Hg 80.3(1)°]. The anion lies close to a centre of symmetry and is linked to its inversion image by one of the chlorine atoms. The reduction in the Hg–Fe–Hg angle from the regular octahedral value is shown to be a consequence of the more extended Fe–Hg relative to the Fe–CO bonds, rather than to Hg ⋯ Hg interactions.

Crystal structure of tetraphenylarsonium cis-tetracarbonyl(chloromercurio)(dichloromercurio)ferrate

The crystal structure of the title compound has been determined by X-ray diffraction (heavy-atom) methods and refined by least squares to R 0.059 for 2 917 observed reflections. Crystals are triclinic P, a = 11.848(3), b= 13.524(4), c= 11.624(3)Å, α= 123.87(2), β= 94.01 (2), γ= 90.91 (2)°, Z= 2. Within the anion, the two mercury atoms are bonded cis in the co-ordination sphere of the six-co-ordinate iron atom [Fe–Hg 2.560(3) and 2.516(4)Å, Hg–Fe–Hg 80.3(1)°]. The anion lies close to a centre of symmetry and is linked to its inversion image by one of the chlorine atoms. The reduction in the Hg–Fe–Hg angle from the regular octahedral value is shown to be a consequence of the more extended Fe–Hg relative to the Fe–CO bonds, rather than to Hg ⋯ Hg interactions.

Basicité des complexes trans-L 2(CO) 3Fe liaisons fer-mercure dans les complexes L 2(CO) 3Fe→HgX 2↔ [L 2(CO) 3Fe-HgX] +X −

L 2(CO) 3Fe, when L is P(OMe) 3, reacts with HgX 2 (X = l, Br, I) to form 1 1 adducts which are formulated, on the basis of infrared spectra and conductivity measurements, as metal donor-acceptor complexes L 2(CO) 3Fe→HgX 2, and 1 4 (X = Cl) or 1 2 (X = Br, I) adducts that dissociate in nitrobenzene solution, affording ionic species [L 2(CO) 3FeHgX] + [HgX 3] −. When L is PMe 3, only 1 1 adducts are formed which are formulated L 2(CO) 3Fe→HgI 2 or [L 2(CO) 3FeHgX] + X − (X = Cl, Br). When L is P(OMe) 3, an equilibrated reaction occurs between the two species L 2(CO) 3Fe→HgX 2 and [L 2(CO) 3FeHgX] + [HgX 3] −, allowing to compare the bonds Fe→Hg and FeHg.

The preparation, reactions, and infrared spectra of some derivatives of bis(tricarbonylnitrosyliron)mercury

Complexes of the type [Hg{Fe(CO)2(NO)L}2][L = R3P, (RO)3P, R3As, and R3Sb; R = alkyl or aryl] have been prepared. They react with mercury(II) halides to give [XHgFe(CO)2(NO)L] derivatives, some of which have been isolated (L = CO and PhEt2As; X = Br and l). The i.r. spectra of both series of compounds indicate that they possess linear L–Fe–Hg–X systems [X = Cl, Br, I, and Fe(CO)2(NO)L] with trigonal bipyramidal co-ordination about the iron atoms. The parent compound, [Hg{Fe(CO)3NO}2], dissociates completely in dimethyl sulphoxide solution to give the [Fe(CO)3NO]–ion. The substituted derivatives do not ionize.

Spektroskopische untersuchungen an komplexverbindungen XI. IR-Spektrum und struktur von Hg[Fe(CO) 3NO] 2

From the infrared spectrum of Hg[Fe(CO) 3NO] 2 a structure with FeHgFe bonding and trigonal bipyramidal coordination of the iron atoms is deduced. The interpretation excludes the possibility that the NO groups are trans to one another. The asymmetric MHgM stretching vibrations of Hg[Fe(CO) 3NO] 2, Hg[Co(CO) 4] 2 and [HgFe(CO) 4] n are found at 200 cm −1.