Synthesis, Structure, and Flash Photolysis Kinetic Studies of Borylated Bis(dioximato)iron(II) Carbonyl Complexes

Silva, D. G. A. Harshani de; Leznoff, Daniel B.; Impey, Gary; Vernik, Isak; Jin, Zhe; Stynes, Dennis V.

doi:10.1021/ic00120a003

Cited by 25 publications

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“…Synthetic Aspects. The following compounds were synthesized by using standard methods: Fe(CO) 3 ( cyclo -butadiene), CpFe(CO) 2 Me, Fe(CO) 3 (propenal), CpFe(CO) 2 Cl, (CO)(pyr)(DMGBPh 2 ) 2 Fe(II) (DMG = dimethylglyoximato), (CO)(pyr)(DMGBBN) 2 Fe(II) (BBN = 9-borabicyclo[3.3.1]nonane), and (CO)(pyr)(5,10,15,20-tetraphenylporphinato)Fe(II) …”

Section: Methodsmentioning

confidence: 99%

“…17,18 Experimental Section Synthetic Aspects. The following compounds were synthesized by using standard methods: Fe(CO)3(cyclo-butadiene), 19 CpFe(CO)2Me, 20 Fe(CO)3(propenal), 21 CpFe(CO)2Cl, 22 (CO)(pyr)(DMGBPh2)2Fe(II) (DMG ) dimethylglyoximato), 23 (CO)(pyr)(DMGBBN)2Fe(II) (BBN ) 9-borabicyclo[3.3.1]nonane), 23 and (CO)(pyr)(5,10,15,20-tetraphenylporphinato)Fe(II). 24 (CO)(1-methylimidazole)(TPP)Fe(II) and (Ph-NO)(pyr)(TPP)Fe(II) (TPP ) 5,10,15,20-tetraphenylporphinato) were both prepared from (TPP)FeCl, and their structures determined crystallographically.…”

Section: Introductionmentioning

confidence: 99%

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An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

et al. 1998

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We have investigated the 57Fe Mössbauer quadrupole splittings in the following compounds by using density functional theory, and in some cases via experiment: Fe(CO)3(cyclo-butadiene), Fe(CO)5, Fe(CO)3(1,4−butadiene), CpFe(CO)2Me, Fe(CO)3(propenal), CpFe(CO)2Cl, (CO)(pyridine)(DMGBPh2)2Fe(II) (DMG = dimethylglyoximato), (CO)(pyridine)(DMGBBN)2Fe(II) (BBN = 9-borabicyclo[3.3.1]nonane), (CO)(1-methylimidazole)(5,10,15,20-tetraphenylporphinato)Fe(II), (CO)(pyridine)(5,10,15,20-tetraphenyl-porphinato)Fe(II), (nitrosobenzene)(pyridine)(5,10,15,20-tetraphenylporphinato)Fe(II), (pyridine)2(5,10,15,20-tetraphenylporphinato)Fe(II), (1-methylimidazole)2(5,10,15,20-tetramesitylporphinato)Fe(II), and (trimethylphosphine)2(2,3,7,8,12,13,17,18-octaethylporphinato)Fe(II). The electric field gradients at iron were evaluated by using a locally dense basis approach: a Wachters' all electron representation for iron, a 6-311++G2d basis for all atoms directly bonded to iron, and either a 6-31G* basis for all other atoms or, in the case of the metalloporphyrins, a 6-31G*/3-21G* or 4-31G* basis, with the smaller basis being used on the peripheral atoms. Using a value of 0.16 × 10-28 m2 for the quadrupole moment of 57Fem, we find good agreement between theoretical and experimental quadrupole splittings: a slope of 1.04, an R 2 value of 0.975, and a root-mean-square error of 0.18 mm s-1, for the 14 compounds examined. We have also investigated the effects of the CO ligand tilt and bend on the 57Fe quadrupole splittings in several heme models. The theoretical results provide no support for the very large (40°) Fe−C−O bond angles suggested by several diffraction studies on Physeter catodon carbonmonoxymyoglobin (P21 crystals). In contrast, the experimental results for (CO)(1-MeIm)(5,10,15,20-tetraphenylporphinato)Fe(II), which contains a linear and untilted Fe−CO, are in very close accord with the experimental values for CO-myoglobin: 0.35 mm s-1 for the model system versus 0.363−0.373 mm s-1 for MbCO, with V zz oriented perpendicular to the porphyrin plane, as found experimentally. Calculations on metalloporphyrins at the more distorted X-ray geometries yield quadrupole splittings around 2 mm s-1, inconsistent with experiment.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

et al. 1998

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“…We present here the synthesis and crystal structure of a bis-(diethylglyoximato)nickel(II) complex, with one 9-borabicyclo[3.3.1]nonane (BBN) unit chelated to the O atoms, (I). To the best of our knowledge, BBN adducts of nickel glyoxime complexes have not been reported previously, although some related iron(II) complexes are known (Harshani de Silva et al, 1995). Compound (I) was prepared in good yield by treating bis(diethylglyoximato)nickel(II) with methoxy-9-BBN in toluene.…”

Section: Commentmentioning

confidence: 99%

Mono-BBN (9-borabicyclo[3.3.1]nonane) adduct of bis(diethylglyoximato)nickel(II)

2003

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“…The Fe III/II reduction potentials depend on the axial ligand, ranging from +0.406 V (L = MeIm; linker = BF 2 ) to +1.16 V vs SCE (L = p-toluenesulfonylmethyl isocyanide, BF 2 ). 11 The electrochemistry of several tetraimine iron systems at negative potentials has been investigated, as in the cases of Me 6 [14]-1,3,8,10-cyclotetradecane-N 4 -tetraene (tetraeneN 4 ) and 2,3,9,10-Me 4 -1,4,8,11-N 4 -cyclotetradecanetetraene (tim) iron complexes. 15,16 Indeed, the reduction of [(tim)Fe(MeCN) 2 ] 2+ led to isolation of an unexpected Fe I −Fe I dimer, [{(tim)Fe} 2 ], which was structurally characterized.…”

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confidence: 99%

“…We have begun a program to study catalytic reductions involving diglyoximatoiron(II) species analogous to those reported by Pang and Stynes. − The complexes are macrocyclic species bearing two glyoximato ligands linked by difluoroboronyl (BF 2 ) or diphenylboronyl (BPh 2 ) groups. The Fe III/II reduction potentials depend on the axial ligand, ranging from +0.406 V (L = MeIm; linker = BF 2 ) to +1.16 V vs SCE (L = p -toluenesulfonylmethyl isocyanide, BF 2 ) .…”

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Fe₄ Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF₂)₂Fe(L)₂] (L = MeCN, ^tBuⁱNC)

2012

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We report the syntheses, X-ray structures, and reductive electrochemistry of the Fe II complexes [(dmgBF 2 ) 2 Fe(MeCN) 2 ] (1; dmg = dimethylglyoxime, MeCN = acetonitrile) and [(dmgBF 2 )Fe( t Bu i NC) 2 ] (2; t Bu i NC = tert-butylisocyanide). The reaction of 1 with Na/ Hg amalgam led to isolation and the X-ray structure of [(dmgBF 2 ) 2 Fe(glyIm)] (3; glyIm = glyimine), wherein the (dmgBF 2 ) 2 macrocyclic frame is bent to accommodate the binding of a bidentate apical ligand. We also report the Xray structure of a rare mixed-valence Fe 4 cluster with supporting dmg-type ligands. In the structure of [(dmg 2 BF 2 ) 3 Fe 3 ( 1 / 2 dmg) 3 Fe(O) 6 ] (4), the (dmgBF 2 ) 2 macrocycle has been cleaved, eliminating BF 2 groups. Density functional theory calculations and electron paramagnetic resonance data are in accordance with a central Fe III ion surrounded by three formally Fe II dmg 2 BF 2 units.

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Synthesis, Structure, and Flash Photolysis Kinetic Studies of Borylated Bis(dioximato)iron(II) Carbonyl Complexes

Cited by 25 publications

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An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

Mono-BBN (9-borabicyclo[3.3.1]nonane) adduct of bis(diethylglyoximato)nickel(II)

Fe₄ Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF₂)₂Fe(L)₂] (L = MeCN, ^tBuⁱNC)

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Synthesis, Structure, and Flash Photolysis Kinetic Studies of Borylated Bis(dioximato)iron(II) Carbonyl Complexes

Cited by 25 publications

References 0 publications

An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

An Experimental and Density Functional Theoretical Investigation of Iron-57 Mössbauer Quadrupole Splittings in Organometallic and Heme-Model Compounds: Applications to Carbonmonoxy-Heme Protein Structure

Mono-BBN (9-borabicyclo[3.3.1]nonane) adduct of bis(diethylglyoximato)nickel(II)

Fe4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF2)2Fe(L)2] (L = MeCN, tBuiNC)

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Fe₄ Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF₂)₂Fe(L)₂] (L = MeCN, ^tBuⁱNC)