Arsido iron carbonyl clusters

Zimler, Tamis; Vízi-Orosz, Anna; Markó, László

doi:10.1007/bf01402694

Cited by 7 publications

(1 citation statement)

References 11 publications

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“…A green band identified as Fe 3 (CO) 12 eluted with hexanes. A reddish band identified as Fe 4 (CO) 14 (μ 4 -AsCl) by IR and mass spectrometry was eluted with hexanes/toluene (8/1) …”

Section: Methodsmentioning

confidence: 99%

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)

et al. 1997

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The triiron clusters Fe3(CO)9(μ3-EML n )2 (1 - E, ML n = MnCp(CO)2, E = P, As, Sb; 2 - E, ML n = Cr(CO)5, E = P, As, Sb) can be considered cluster analogues of organopnictane (ER3) ligands, in which the triply bridging E ligands are coordinated to 16-electron capping metal groups, ML n . Structural parameters, infrared CO stretching frequencies, and reduction potentials for this metallopnictane series are reported. Analysis of structural, spectroscopic, and electrochemical data reveal systematic variations as a function of the capping heteroatom and the metal fragment coordinated to the heteroatom. The covalent radius of the capping heteroatom dictates the structure of the Fe3(CO)9(μ3-E)2 bonding framework, and both Fe−E and Fe−Fe distances increase linearly with increasing heteroatom covalent radius. The electronegativity of the capping heteroatom (E) influences the frequencies of the Fe3-core carbonyl stretching modes (νCO(Sb) < νCO(As) < νCO(P)), while the two-electron reduction potentials for the series 1 and series 2 clusters (E 1/2(Sb) > E 1/2(As) > E 1/2(P)) correlate with the covalent radius of E. Clusters with capping Cr(CO)5 groups are reduced at potentials ∼400 mV more positive than the MnCp(CO)2-capped analogues. On the basis of the frequencies of the CO stretching modes for the capping ML n group and the E−ML n distance, the metallopnictance ligands are classified as intermediate between organopnictanes and halopnictanes in terms of their net electronic impact (the sum of σ-donating and π-accepting properties). Results of Fenske−Hall molecular orbital calculations provide a qualitative description of the Fe3−E2 bonding as a function of heteroatom (E). Trends in Mulliken populations and a Walsh analysis suggest the Fe−E bonds are strongest for the most electronegative E, phosphorus. The Fe−Fe overlap populations are nearly constant with E, despite the increase in Fe−Fe distance attendant upon incorporation of larger heteroatoms. Two-electron reduction of the metallopnictane Fe3-core changes the donor and acceptor characteristics of the metallopnictane ligand, as demonstrated by a structure determination for [(PhCH2)Me3N]2(1 - P). The Mn−P distance in (1 - P)2- is 0.1 Å longer than in the neutral analogue, 1 - P. Single-crystal X-ray structure determinations for 1 - As, 1 - Sb, 2 - P, 2 - As, 2 - Sb, and [(PhCH2)Me3N]2(1 - P) are reported.

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“…A green band identified as Fe 3 (CO) 12 eluted with hexanes. A reddish band identified as Fe 4 (CO) 14 (μ 4 -AsCl) by IR and mass spectrometry was eluted with hexanes/toluene (8/1) …”

Section: Methodsmentioning

confidence: 99%

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)

et al. 1997

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Komplexe mit substituentenfreien acyclischen und cyclischen Phosphor‐, Arsen‐, Antimon‐ und Bismutliganden

Scherer

1990

Angewandte Chemie

183

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Professor Max Schmidt zum 65. Geburlstag gewidmetUnter Phosphor-, Arsen-, Antimon-und Bismutliganden verstand man bis vor kurzem fast ausschliel3lich Verbindungen wie R,E, R,E(CH,),ER, und RC[(CH,),ER,], (E = P,As,Sb,Bi), deren freies Elektronenpaar am E-Atom als 2e-Donor fungiert. Das Forschungsinteresse gilt aber zunehmend den substituentenfreien En-Liganden (n = 1 -6), die bevorzugt aus EX,(X = F,CI,Br,Ph), E(SiMe,),, (RAs),, P,S,, As,S,, grauem Arsen und vor allem P4 und As, erhaltlich sind und die in Gegenwart bestimmter Ubergangsmetallkomplexfragmente koordinativ stabilisiert werden konnen. In Zwei-und Dreikernkomplexen rnit PI-, As,-und Sb,-Liganden treten M-E-Mehrfachbindungsanteile auf. E-Atome konnen aber auch teilweise oder vollstandig in Hohlraumen der unterschiedlichsten Metallcluster eingeschlossen sein.Besonders haufig entstehen Metallatetrahedrane mit bis zu drei E-Atomen. Die mit Abstand groDte Koordinationsvielfalt weisen neben den El-die E,-Liganden auf, denen man sowohl in Form intakter Tetraeder als auch als Bestandteile von Ketten, Polycyclen, Wiirfeln und eines trigonalen Prismas begegnet. Die zu den carbocyclischen (CH),-n-Systemen isoelektronischen Phosphor-und Arsenanaloga cyclo-En eignen sich als Liganden fur Sandwich-(n = 3,4,5) und Tripeldeckerkomplexe (n = 3,5,6). Nicht zuletzt sind diese Verbindungen aufgrund ihrer Reaktivitat und der Parallelen zur Organischen Chemie und Festkorperchemie bei Chemikern verschiedener Disziplinen auf reges Interesse gestoBen.

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Complexes with Substituent‐free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands

Scherer

1990

Angew. Chem. Int. Ed. Engl.

271

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Dedicated to Professor Max Schmidt on the occasion of his 65th birthday Until recently, phosphorus, arsenic, antimony and bismuth ligands were nearly always understood to be molecules such as R,E, R,E(CH,),ER,, and RC[(CH,),ER,],(E = P, As, Sb, Bi) in which the lone pair of the atom E functions as a 2e donor. Current research interests, however, increasingly involve substituent-free En ligands (n = 1 -6), the various types ofwhich are mainly accessible via EX, (X = F,CI,Br,Ph), E(SiMe,),, (RAs),, P,S,, As,S,, gray arsenic, and especially P, and As,; these ligands can be stabilized in the coordination spheres of certain transition metal fragments. P,, As, and Sb, units with multiple M-E bonds are found in bi-and trinuclear complexes; E, units can also be encapsulated (partially or completely) in cavities of a variety of metal cluster frameworks. Metallatetrahedranes with up to three E atoms are especially common. Besides E, units, the greatest variety of coordination modes is exhibited by E, ligands, which are found as intact tetrahedra and also as parts of chains, polycycles, cubes and a trigonal prism. The phosphorus and arsenic species cyclo-En, isoelectronic to the carbocyclic (CH), species, are suitable ligands for forming sandwich complexes (n = 3,4, 5) and triple-decker sandwich complexes (n = 3, 5, 6). In addition to the wide variety of chemical reactions, remarkable parallels are found in organic chemistry as well as in solid-state chemistry for many of these substance classes. Some of the molecules have received lively interest from theoretical chemists.

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Arsido iron carbonyl clusters

Abstract: The XAsFe4 (CO)i4 (X = CI, Br) clusters have been prepared and characterised and a new synthesis under mild conditions has been found for As2Fea (CO)9. The latter complex has at least two isomeric structures in solution.

Cited by 7 publications

References 11 publications

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)

Komplexe mit substituentenfreien acyclischen und cyclischen Phosphor‐, Arsen‐, Antimon‐ und Bismutliganden

Complexes with Substituent‐free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands

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Arsido iron carbonyl clusters

Abstract: The XAsFe4 (CO)i4 (X = CI, Br) clusters have been prepared and characterised and a new synthesis under mild conditions has been found for As2Fea (CO)9. The latter complex has at least two isomeric structures in solution.

Cited by 7 publications

References 11 publications

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe3(CO)9(μ3-EMLn)2(E = P, As, Sb; MLn= Cr(CO)5, MnCp(CO)2)

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe3(CO)9(μ3-EMLn)2(E = P, As, Sb; MLn= Cr(CO)5, MnCp(CO)2)

Komplexe mit substituentenfreien acyclischen und cyclischen Phosphor‐, Arsen‐, Antimon‐ und Bismutliganden

Complexes with Substituent‐free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands

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Product

Resources

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Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)

Structures, Bonding, Infrared Spectroscopy, and Two-Electron Reduction Potentials of the Coordinated Metallopnictanes Fe₃(CO)₉(μ₃-EML_n)₂(E = P, As, Sb; ML_n= Cr(CO)₅, MnCp(CO)₂)