Preparation and probable structure of 1,2-bis(dimethylarsino)-3,3,4,4-tetrafluorocyclobutene triiron decacarbonyl complex

Cullen, William R.; Harbourne, D. A.; Liengme, Bernard V.; Sams, J. R.

doi:10.1021/ja01014a088

Cited by 16 publications

(9 citation statements)

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“…Preparations of the ligands ffos, fefos, and ffars have been previously reported. [3][4][5][6][7] The known complexes diphosFe(CO)3, diphosFe2-(CO)s, and diarsFe(CO)¡¡ were prepared by methods similar to those previously described.1•1'16'8 The preparations of the fluorocarbon complexes described below are selected from a number of related experiments8 and give the optimum conditions so far found for obtaining the particular compound. Spectroscopic data for the complexes are listed in Tables I-VI (a) ffosFe(CO)3.-Iron pentacarbonyl (4.4 g, 22.4 mmol), ffos (0.4 g, 0.81 mmol), and acetone (10 ml) were sealed under vacuum in a thick-walled Pyrex tube.…”

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confidence: 99%

Five-coordinate iron carbonyl complexes with fluorocarbon-bridged ligands

Cullen¹,

Harbourne²,

Liengme³

et al. 1969

Inorg. Chem.

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P(OCeH5)3] with iodine in dichloromethane was shown by infrared spectroscopy to afford a third product in addition to x-C5H6Fe(CO)2I and x-C6H6Fe(CO)LI; these three compounds were formed in approximately equal amounts. When this iodination was performed in benzene, however, the unknown product separated out while trace quantities of x-CsH5Fe(CO)2I and x-CóH5Fe(CO)LI remained in the benzene solution. The precipitate was shown to be ionic and characterization of the tetraphenylborate derivative showed it to be [x-C5H6Fe(CO)2L]B(CeH6)4. The neutral compounds x-C5H6Fe(CO)LI were identified by comparing their infrared spectra with the spectra of authentic samples previously synthesized from x-C6H6Fe(CO)2l.2SThe physical and spectroscopic data for the ionic complexes are given in the tables. Conductivity data and spectroscopic evidence show, respectively, these derivatives to be 1:1 electrolytes in acetone and diamagnetic. The infrared spectra of these compounds in solution contain two peaks corresponding to C-0 stretching modes; the frequencies decrease with the increase of the over-all ( -) donor ability of the phos-(28) A. L. du Preez, M.S. Thesis, University of Pretoria.Inorganic Chemistry phorus donor ligand as expected. The single cyclopentadienyl proton resonance in the nmr spectra of these ionic compounds is split into a doublet due to phosphorus-hydrogen coupling. The coupling constant could only be measured for the compounds containing the ligands P(C2H3)3 and P(0-f-CsH7)3.The formation of both ionic and neutral compounds in the iodination of the monosubstituted derivatives demonstrates that this reaction occurs by at least two mechanistic pathways, one involving a symmetric cleavage and the other an asymmetric cleavage of the dinuclear parent. A similar scheme has been proposed for the halogenation of [x-C6HóFe(CO)2]2 on the basis of the isolation of [x-C6H6Fe(CO)3 ]X and x-CsHjFe-(CO)2X (X = halogen) from the reaction mixture.29Acknowledgments.-The authors express their gratitude to Dr. K. G. R. Pachler, National Chemical Research Laboratory, CSIR, Pretoria, South Africa, for the measurement of the nmr spectra. A. L. du P. thanks the South African Council for Scientific and Industrial Research and the University of Pretoria for financial support.

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confidence: 99%

Five-coordinate iron carbonyl complexes with fluorocarbon-bridged ligands

Cullen¹,

Harbourne²,

Liengme³

et al. 1969

Inorg. Chem.

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“…The disposition of coordinating atoms about the rhodium in both cation and anion is approximately square planar. The bite of the ligand as measured by the intra-ligand P-P distance is 3.111 (8) A. Cation and anion are so packed together than the terminal atoms of the anion are directed toward the adjacent cation, as illustrated in Fig. 2.…”

Section: Structure Solutionmentioning

confidence: 99%

“…As a part of a program to investigate the reactions of fluorocarbon-bridged tertiary diphosphines and diarsines with transition metals (1)(2)(3)(4)(5)(6)(7)(8)(9), the reactions between these ligands and chlorodicarbonyl rhodium dimer were studied. The intention was to prepare simple monocar-bony1 complexes of the type LRh(C0)Cl (L is a chelating ditertiary diphosphine), and to study the ability of the ligands to stabilize these complexes with respect to oxidative addition (1).…”

Section: Crystal Datamentioning

confidence: 99%

The Crystal Structure of [Rh(f₆fos)₂]⁺[cis-(CO)₂RhCl₂]⁻

Einstein¹,

Hampton²

1971

Can. J. Chem.

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The crystal structure of di(1,2-bis(diphenylphosphino)hexafluorocyclopentene) rhodium(I) cis-dicarbonyldichlororhodate(I), [Rh(f6fos)2][cis-Rh(CO)2Cl2] has been determined from three-dimensional X-ray scintillation counter data. The structure has been refined by full-matrix least-squares techniques to a conventional R factor of 8.8%. The salt crystallizes in the tetragonal space group I41/a with eight formula units in a cell of dimensions a = 17.722(1) Å and c = 36.773(4) Å. Each ion is nearly square planar and has a crystallographic two-fold axis passing through the rhodium atom. The two independent Rh—P distances are 2.282(6) and 2.300(6) Å, and the bite of the chelating ditertiary phosphine, f6fos, is 3.111(8) Å as measured by the intra-ligand P—P distance.

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“…As part of our continuing study of the reactions of fluorocarbon-bridged ditertiary phosphines and arsines (4)(5)(6)(7)(8), 3, we have prepared a number of Rh(1) complexes which present some interesting parallels with and differences from earlier studies. Herein we report the results of this work.…”

Section: Introductionmentioning

confidence: 98%