Complexes of polypyrazolylborate ligands. V. Characterization of acety(tri-1-pyrazolylborato)(dicarbonyl)iron, (HBpz3)(COCH3)(CO)2Fe, in solution and in the crystal

Cotton, F. Albert; Frenz, B. A.; Shaver, Alan

doi:10.1016/s0020-1693(00)94803-5

Cited by 48 publications

(10 citation statements)

References 18 publications

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“…NMR monitoring of the reaction revealed that the acyl complexes are formed via the corresponding diamagnetic alkyl dicarbonyl complexes [Tp¢Fe(CO) 2 R]. 31 Parkin et al have shown 32 that for very bulky scorpionate ligands the iron methyl group is highly reactive towards CO as illustrated in Scheme 15. [(PhTp tBu )FeMe] reacts with CO at 120 • C. However, instead of CO insertion into the Fe-C bond, reduction takes place and the novel 15-electron four-coordinate monovalent iron(I) carbonyl complex [(PhTp tBu )Fe(CO)] is formed.…”

Section: Scheme 12mentioning

confidence: 99%

Reactivity of coordinatively unsaturated iron complexes towards carbon monoxide: to bind or not to bind?

et al. 2011

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An overview of the reactivity of coordinatively unsaturated iron complexes (in most cases Fe(II)) towards carbon monoxide is presented. Unsaturated iron complexes are known with coordination numbers (CN) of two to five adopting linear or slightly bent (CN = 2), trigonal (CN = 3), tetrahedral, square planar or trigonal pyramidal (CN = 4), and square-pyramidal or trigonal-bipyramidal geometries (CN = 5), respectively. The binding of CO depends strongly on the number and the nature of co-ligands (overall ligand field strength), the charge of the complex, the complex geometry, and the spin state of the unsaturated metal center. In many cases, CO addition to high-spin iron complexes takes place with concomitant spin state changes forming compounds in the lowest possible spin state, i.e., with S = 0. In several other cases, however, the addition of CO is reversible or is even totally rejected altogether for either thermodynamic or kinetic reasons. In the case of the latter such reactions are termed "spin-blocked" or "spin forbidden".

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Section: Scheme 12mentioning

confidence: 99%

Reactivity of coordinatively unsaturated iron complexes towards carbon monoxide: to bind or not to bind?

et al. 2011

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“…‡ The diamagnetic iron complex 3a was characterized on the basis of its 1 H and 13 C NMR spectra indicating the (CO) 2 Fe-C(NO)CH 2 CH 3 functional group in addition to the k 3 -Tp iPr ligand, and its IR spectrum suggests the presence of two rotamers as observed for TpFe(CO) 2 -C(NO)CH 3 . 5 The assignment of the monocarbonyl structure of the cobalt complex 3b is based on the single n(CO) absorption. Interestingly, although the ethylnickel complex 2c could not be isolated from the Grignard reaction mentioned above, the reaction under CO atmosphere produced the acyl complex 3c, which was characterized spectroscopically and structurally [Fig.…”

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confidence: 99%

Thermally stable coordinatively unsaturated alkyl complexes resistant to β-hydride elimination: TpiPrM–CH2CH3 (M = Co, Fe)

Shirasawa¹,

Akita²,

Hikichi³

et al. 1999

Chem. Commun.

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“…A similar effect was observed in TpFe{C(O)Me}(CO) 2 , which represents the only report of a single-crystal diffraction study of a tris(pyrazolyl)borate iron acetyl compound. That species formed in 8% isolated yield . Tp i Pr2 Fe{C(O)R}(CO) 2 (R = CH 2 C 6 H 4 Me, Et) and Tp Me3 Fe{C(O)R}(CO) 2 (Tp Me3 = HB(N 2 C 3 Me 3 ) 3 ) form in good (ca.…”

Section: Results and Discussionmentioning

confidence: 99%

“…That species formed in 8% isolated yield. 33 Tp iPr2 Fe{C(O)R}(CO) 2 (R = CH 2 C 6 H 4 Me, Et) and Tp Me3 Fe{C(O)R}(CO) 2 (Tp Me3 = HB(N 2 C 3 Me 3 ) 3 ) form in good (ca. 60%) yields, 34 while tBuTp iPr Fe{C(O)Me}(CO) 2 (tBuTp iPr = tBuB(3-N 2 C 3 -iPrH 2 ) 3 ) was not isolable in pure form.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Heteroleptic Four-Coordinate Tris(oxazolinyl)borato Iron(II) Compounds

2019

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The reaction of FeBr 2 and 1 equiv. of thallium tris(4,4-dimethyl-2oxazolinyl)phenylborate (TlTo M ) in THF provides To M FeBr (1), whereas FeBr 2 and 2 equiv. of TlTo M react to give (To M ) 2 Fe (2). Two ν CN bands at 1604 and 1548 cm -1 indicated bidentate coordination of To M to iron in 2. Homoleptic 2 and FeBr 2 react in THF overnight through an unusual comproportionation process to give compound 1, which is apparently the thermodynamic product. The salt metathesis reaction of 1 and KCH 2 Ph affords To M FeCH 2 Ph (3).The effective magnetic moments of compounds 1 -3 range from 4.9 to 5.4  B , and these values are consistent with high-spin iron(II) (S = 2). A single 1 H NMR signal assigned to the methyl groups of the To M ligand suggested tridentate coordination of the To M ligand to iron in 1 and 3.X-ray crystallography studies of 1 -3 establish their structure as four-coordinated tetrahedral iron complexes. To M FeBn and CO (1 atm) react to afford isolable To M Fe{C(=O)Bn}(CO) 2 (4) as a yellow solid. Complex 4 is diamagnetic (S = 0), and the three distinct methyl signals in the 1 H

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Complexes of polypyrazolylborate ligands. V. Characterization of acety(tri-1-pyrazolylborato)(dicarbonyl)iron, (HBpz3)(COCH3)(CO)2Fe, in solution and in the crystal

Cited by 48 publications

References 18 publications

Reactivity of coordinatively unsaturated iron complexes towards carbon monoxide: to bind or not to bind?

Reactivity of coordinatively unsaturated iron complexes towards carbon monoxide: to bind or not to bind?

Thermally stable coordinatively unsaturated alkyl complexes resistant to β-hydride elimination: TpiPrM–CH2CH3 (M = Co, Fe)

Heteroleptic Four-Coordinate Tris(oxazolinyl)borato Iron(II) Compounds

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