38903-71-8Relevant academic research and scientific papers
Novel Cluster Frameworks from the Reactions of the Unsaturated Clusters Fe4(CO)11(μ4-PR)2 with Alkynes
Jaeger, J. Tilman,Powell, Anne K.,Vahrenkamp, Heinrich
, p. 1729 - 1738 (2007/10/02)
The unsaturated clusters Fe4(CO)11(μ4-PR)2 (1-3, R = Ph, p-Tol, t-Bu) react with terminal alkynes primarily by insertion of the alkyne between one phosphorus and two iron atoms.The structure analysis of Fe4(CO)11(μ4-PTol)4-P(Tol)CMeCH> and NMR studies in solution show that the insertion products exist as two isomers, which differ by the orientation of the alkyne (P-CR-CH-Fe/P-CH-CR-Fe), and whose interconversion in solution can be catalyzed by bases.Starting from 3, additionally and preferentially alkyne-containing clusters are formed with CO elimination, which contain a novel Fe4P2C2 framework that can be derived from a pentagonal bipyramid with an equatorial Fe2PC2 unit as evidenced by the structure determination of Fe4(CO)9(μ3-P-tBu)4-P(tBu)CHCMe>.The primary alkyne-insertion products are easily induced by an excess of donor ligands or by iodine oxidation to eliminate one ironcarbonyl unit and form the clusters Fe3(CO)93-μ3-P(R)CHCR'PR> and substituted derivatives thereof.For these the structure analysis of the (PhPCHCMePPh) compound proves the PCCP sequence and a side-on coordination of the C2 unit to one iron atom.The degradation with P(OMe)3 and tBuNC produces as intermediates the substitution derivatives Fe4(CO)10L(μ4-PPh)4-P(Ph)CRCH>, which also exist as two isomers with different orientation of the CR-CH unit.
DIHALOGENPHOSPHANCOMPLEXE ALS METALLORGANISHE SYNTHESEBAUSTEINE
Lang, Heinrich,Zsolnai, Laszlo,Huttner, Gottfried
, p. 23 - 52 (2007/10/02)
The dichlorophosphanes (R)P(Cl)2 react with Fe2(CO)9 to give (CO)4Fe-P(R)(Cl)2 (I) in high yields.When treated with Fe2(CO)9 in 2.5 M excess, compounds I give the μ2-chloro-μ2-chlorophosphido-bridged dinuclear molecules II, Fe2(CO)6(μ2-Cl)(μ2-PRCl).Further treatment of II with Fe2(CO)9 resulsts in the formation of the trinuclear clusters IV, Fe3(CO)10(μ3-PR).Zinc reduction of II leads to V, Fe4(CO)11)(μ4-PR)2.All of these reactions lead to fairly high yields for a variety of substituents R.The product selectivity is effectively controlled by the stoichiometry.The syntheses and properties of the main products I,II,IV and V, as well as those of the dinuclear side-products 2-PRCl)>2 (III), 2-PRCl)>2 (VI), and the trinuclear species (CO)9Fe3(μ3-PR)2 (VII), are discussed.
(μ-H)2M3(CO)8(μ-PPh 2)2 (M = Fe, Ru, Os): An isostructural triad of phosphido-bridged hydrides. Rational synthesis and structural characterization
Patel, Vikram D.,Cherkas, Andrew A.,Nucciarone, Donato,Taylor, Nicholas J.,Carty, Arthur J.
, p. 1792 - 1800 (2008/10/08)
The synthesis and structural characterization of the triad of phosphido-bridged hydrido clusters (μ-H)2M3(CO)8(μ-PPh2) 2 (1, M = Fe, 2, M = Ru, and 3, M = Os) are described. The triiron cluster 1 has been prepared via the reaction of Ph2PH with the protonated anion Fe4(CO)132-. The ruthenium and osmium congeners have been obtained from the phosphine complexes M3(CO)10(PPh2H)2 via oxidative addition of the P-H bonds of the secondary phosphines to the clusters. Crystals of 1-3 are triclinic of space group P1 with unit cell dimensions. 1: a = 10.918 (2) A?, b = 11.898 (2) A?, c = 14.705 (2) A?; α = 75.02 (1)°, β = 84.72 (1)°, γ = 70.84 (1)°. 2: a = 11.150 (1) A?, b = 12.027 (1) A?, c = 14.693 (1) A?; α = 76.03 (1)°, β = 84.70 (1)°, γ = 70.24 (1)°. 3: a = 11.184 (1) A?, b = 11.991 (1) A?, c = 14.657 (1) A?; α = 76.17 (1)°, β = 84.72 (1)°, γ = 70.01 (1)°. The structures were solved and refined to the following R and Rw values; 1, R = 0.034, Rw = 0.039 on 4243 observed (I ≥ 3σ(I)) data; 2, R = 0.023, Rw = 0.027 on 5478 data; 3, R = 0.038, Rw = 0.048 on 5325 data. The three molecules are isostructural with a triangular framework of metal atoms supported on two adjacent sides by phosphido and hydrido bridges, one metal-metal vector being unbridged. The change in structural parameters down the triad and reactions with carbon monoxide are discussed.
REAKTIONEN KOORDINIERTER LIGANDEN. X. REKTIVITAET ZWEIKERNIGER EISENCARBONYLKOMPLEXE MIT SEKUNDAEREN PHOSPHIDOBRUECKEN μ-RPH
Bartsch, Rainer,Hietkamp, Sibbele,Morton, Stephen,Stelzer, Othmar
, p. 263 - 274 (2007/10/02)
The reaction between pentacarbonyliron(0) and phenylphosphane affords, depending on the conditions applied, the complexes (CO)4FePhPH2 (I), (CO)6Fe2(PhPH)2 (II) or 3(PhP)2 (III) in high yields and purity.Compound I reacts with (η-C5H5)Fe(CO)2Br i
