Synthesis and Structures of Hypervalent Antimony Compounds Bearing an Antimony−Group 6 Transition Metal Bond

Toyota, Koichiro; Yamamoto, and Yohsuke; Akiba, Kin‐ya

doi:10.1021/om000791d

Cited by 18 publications

(4 citation statements)

References 17 publications

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“…To gain insight on the effect of different transition metal fragments on the pseudorotational barrier, hypervalent antimony compounds bearing a group 6 fragment were prepared and the pseudorotational barriers will be discussed in the following paper …”

Section: Resultsmentioning

confidence: 99%

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

et al. 2000

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Diastereomeric pentacoordinate hypervalent stiboranes with an Sb−Fe bond {4a and 4b: RfRfm*Sb*FeCp(CO)2 {Rf = o-C6H4C(CF3)2O-, Rfm* = o-C6H4C*(CF3)(Me)O-} were synthesized by the reaction of stiboranide anion, RfRfm*Sb*-Li+ (3-Li), with CpFeI(CO)2 in the presence of AgBF4. The carbonyl group of 4 was replaced with triphenylphosphine by irradiation with a tungten lamp to give a mixture of four diastereomers {5a−5d: RfRfm*Sb*Fe*Cp(CO)(PPh3)}. Each of the diastereomers was separated by TLC, and the relative stereochemistry was determined by X-ray crystallographic analysis. The thermal equilibration from the pure diastereomer of 5 indicated that the isomerization took place through inversion (pseudorotation) at the central antimony atom. The pseudorotational barriers of 5 were much higher than those of Rf2Sb*Cl and RfRfm*Sb*(p-CH3C6H4). These results are consistent with the electron-donating properties of the group 8 transition metal fragment. Hypervalent stiboranes {6, Rf2Sb*Fe*Cp(CO)(PMe3); 7, Rf2Sb*Fe*Cp(CO)(PEt3)} were also prepared by similar procedures. The order of pseudorotational barriers [2 {Rf2Sb*Fe*Cp(CO)(PPh3)} (32.8, 33.2 kcal/mol) > 7 (32.5, 32.9 kcal/mol) > 6 (32.2, 32.7 kcal/mol)] suggests that the steric effect of the iron ligand also played a role. The pseudorotational barriers of the corresponding ruthenium compounds, RfRfm*Sb*RuCp(CO)2 (12a and 12b), were slightly higher than those of the corresponding iron compounds (4a and 4b).

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Section: Resultsmentioning

confidence: 99%

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

et al. 2000

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“…This is well explained by the increased equatophilicity for the iron fragment resulting from the strong electron-donating power. The large barriers for RfRfm*SbMoCp(CO) 3 and RfRfm*SbMCp(CO) 2 (M = Fe, Ru) [12,13] are also explained by the high equatophilicity. There is, however, a discrepancy between the order of the energy barrier and the donor power implied from the Mössbauer spectra.…”

Section: Relation Between Donor Power and Molecular Structurementioning

confidence: 94%

¹²¹Sb Mössbauer Spectra of Hypervalent Complexes Having an Antimony-transition Metal Bond and Partial Quadrupole Coupling Constants

Takahashi

Ishiguro

Maeda

et al. 2002

Zeitschrift Für Naturforschung A

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Antimony-121 Mössbauer spectra for hypervalent pentacoordinate antimony compounds having Sb-transition metal bond [Rf 2 SbMCp(CO) RfH = o-C 6 H 4 C(CF 3 ) 2 OH , M = Fe, Ru, Cr, Mo, W , Rf 2 SbFeCp(CO)PPh 3 , Rf 2 SbFeCp(dppe)] and closely related compounds Rf 2 SbTol (Tol = p-CH 3 C 6 H 4 ), Rf 2 SbX (X = Cl, Br) are described. The strong -donor power of the metal fragments is demonstrated by the Mössbauer parameters. The -donor power decreases in the order FeCp(dppe) > FeCp(CO)PPh 3 > FeCp(CO) 2 > RuCp(CO) 2 > CrCp(CO) 3 > MoCp(CO) 3 > WCp(CO) 3 Tol. The essential trends in the molecular structure and the Berry pseudorotation are interpreted by this order. In addition, the 2 values for 32 hypervalent antimony compounds are successfully calculated using the additivity model for the 2 value. A unique electronic feature for Rf 2 SbX is clarified through the calculation

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“…Also photoreactions to substitute PR 3 for the CO group were shown to be successful for several SbM (group 6) compounds. The structures of all these products were determined by X‐ray analysis 119.…”

Section: Hypervalent Ate Complexes Of Antimony and Bismuth And Their mentioning

confidence: 99%

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

Akiba¹

2011

Heteroatom Chemistry

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Synthesis and Structures of Hypervalent Antimony Compounds Bearing an Antimony−Group 6 Transition Metal Bond

Cited by 18 publications

References 17 publications

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

¹²¹Sb Mössbauer Spectra of Hypervalent Complexes Having an Antimony-transition Metal Bond and Partial Quadrupole Coupling Constants

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

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Synthesis and Structures of Hypervalent Antimony Compounds Bearing an Antimony−Group 6 Transition Metal Bond

Cited by 18 publications

References 17 publications

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

121Sb Mössbauer Spectra of Hypervalent Complexes Having an Antimony-transition Metal Bond and Partial Quadrupole Coupling Constants

Studies on hypervalent compounds and synthetic work using heteroaromatic cations

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¹²¹Sb Mössbauer Spectra of Hypervalent Complexes Having an Antimony-transition Metal Bond and Partial Quadrupole Coupling Constants