Organonitrogen derivatives of metal carbonyls.  VI.  Novel products reactions of 2-bromo-2-nitrosopropane with metal carbonylanions

King, R. B.; Douglas, W. M.

doi:10.1021/ic50136a018

Cited by 44 publications

(20 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Here we show that aldoximes readily bind to iron(II) porphyrins with formation of Fe(II)(porphyrin)(aldoxime) 2 complexes in which aldoxime binds to the iron via its nitrogen atom. These data give a firm basis for the structure proposed for P450−aldoxime complexes and describe the first example of iron−aldoxime complexes exhibiting such a coordination mode …”

Section: Discussionmentioning

confidence: 55%

New Catalytic Properties of Iron Porphyrins: Model Systems for Cytochrome P450-Catalyzed Dehydration of Aldoximes

et al. 1998

View full text Add to dashboard Cite

Various iron porphyrin systems were found to catalyze the dehydration of aldoximes, such as heptanaldoxime or phenylacetaldoxime, into the corresponding nitriles under mild conditions (t ) 20 °C, neutral or slightly acidic pH). In all these systems, the presence of both the iron porphyrin catalyst and a reducing agent is required, indicating that the active species is the iron(II) porphyrin. The most efficient systems used either an organosoluble iron porphyrin, such as Fe(OEP), in the presence of a carboxylic acid and zinc amalgam as reducing agent, or a water-soluble heme fragment of cytochrome c (microperoxidase MP-11) in the presence of dithionite. The catalytic activity of the systems was greatly increased when using electron-rich iron porphyrins bearing an electron-donating axial ligand, such as imidazole, and a carboxylic acid cocatalyst in close proximity to the iron center. The activity of the best systems was comparable to that of microsomal cytochromes P450 (between 1 and 10 turnovers per min). The intermediate (porphyrin)iron-aldoxime complex formed in those dehydration reactions was isolated in the case of Fe(meso-tetra(2,6-dichlorophenyl)-β-octachloroporphyrin) [meso-tetra(2,6-dichlorophenyl)-β-octachloroporphyrin ) TDCPCl 8 P] and characterized by elemental analysis and UV-visible and 1 H NMR spectroscopy. Comparison of the 1 H NMR spectra of Fe(TDCPCl 8 P)(CH 3 -CHNOH) 2 and Fe(TDCPCl 8 P)(pyridine) 2 strongly indicates that acetaldoxime is bound to iron(II) via its nitrogen atom in the former. A mechanism for iron porphyrin-catalyzed dehydration of aldoximes based on all these results is proposed. It involves a partial charge transfer from electron-rich Fe(II) to the aldoxime CdNOH moiety, which favors the departure of its OH group assisted by an acid cocatalyst. This illustrates the potential of iron porphyrins as catalysts for new reactions very different from the redox transformations for which they are well-known.

show abstract

Section: Discussionmentioning

confidence: 55%

New Catalytic Properties of Iron Porphyrins: Model Systems for Cytochrome P450-Catalyzed Dehydration of Aldoximes

et al. 1998

View full text Add to dashboard Cite

show abstract

“…through acetone and replaces not only the labile tht ligand but also the chloro ligand in [AuCl(tht)The rapid formation of 10 compared to that of[Au(NHCMe 2 )L] or [Au(NHCMe 2 ) 2 ] (1 h, 2 ± 5 h, 5 days, respectively) means that acetimine rapidly forms and condenses to acetonine in the reaction between ammonia and acetone, whereas formation of acetimine from ammonia coordinated to gold(i) is a slow process, especially in the case of both ammonia molecules in [Au(NH 3 ) 2 ] .The reaction of 10 with triphenylphosphane in 1:1 or 1:2 molar ratio results in the displacement of one or both acetonine ligands to give [Au(acetonine)(PPh 3 )]ClO 4(11) or[Au(PPh 3 ) 2 ]ClO 4 , respectively. Complex 11 was also obtained, along with other unidentified species, when NH 3 was bubbled through acetone solutions of 1 a or [Au(PPh 3 )(Me 2 CO)]ClO 4 .…”

mentioning

confidence: 99%

The First Acetimine Gold(I) and Gold(III) Complexes and the First Acetonine Complexes

et al. 2001

View full text Add to dashboard Cite

Ketimino(phosphino)gold(I) complexes of the type [Au[NR=C(Me)R']L]X (X = ClO4, R = H, L = PPh3, R'=Me (la), Et (2a); L=PAr3 (Ar=C6H4OMe-4), R'=Me (1b), Et (2b); L=PPh3, R=R'=Me (3); X= CF3SO3 (OTf), L=PPh3, R=R'=Me (3'); R=Ar, R'=Me (4)) have been prepared from [Au(acac)L] (acac = acetyl acetonate) and ammonium salts [RNH3]X dissolved in the appropriate ketone MeC(O)R'. Complexes [Au(NH=CMe2)2]X (X = C1O4 (6), OTf (6')) were obtained from solutions of [Au(NH3)2]X in acetone. The reaction of 6 with PPN[AuCl2] or with PhICl2 gave [AuCl(NH=CMe2)] (7) or [AuCI2(NH=CMe2)2]ClO4 (8), respectively. Complex 7 was oxidized with PhICl2 to give [AuCl3(NH=CMe2)] (9). The reaction of [AuCl(tht)] (tht = tetrahydrothiophene), NaClO4, and ammonia in acetone gave [Au(acetonine)2]ClO4 (10) (acetonine = 2,2,4,4,6-pentamethyl-2,3,4,5-tetrahydropyrimidine) which reacted with PPh3 or with PPN[AuCl2] to give [Au(PPh3)(acetonine)]ClO4 (11) or [AuCl(acetonine)] (12), respectively. Complex 11 reacts with [Au(PPh3)(Me2CO)]ClO4 to give [(AuPPh3)2(mu-acetonine)](ClO4)2 (13). The reaction of AgClO4 with acetonine gave [Ag(acetonine)(OClO3)] (14). The crystal structures of [Au(NH2Ar)(PPh3)]OTf (5), 6' and 10 have been determined.

show abstract

“…The Fe-N(2) distance of 1.982 (5) Á is within the range previously observed for Fe-N single bond distances in nitrogen-bridged bis(tricarbonyliron) species. 30 The Fe-0 distance of 1.952 (4) Á is likewise a reasonable single bond value; it is marginally shorter than the distance of 1.967 (5) A observed in the CóHsCO-bridged complex.…”

Section: Description Of the Structure And Discussionmentioning

confidence: 89%

Crystal and molecular structure of a bis(tricarbonyliron) complex containing bridging isopropylidenamido and 2-propanoximato(O, N) ligands

Khare¹,

Doedens²

1976

Inorg. Chem.

View full text Add to dashboard Cite

The structure of g-isopropylidenamido-u-2-propanoximato(0,7V)-bis(tricarbonyliron) has been determined by a crystallographic study. Crystals of this complex are triclinic, space group Pi, with reduced cell parameters a = 12.061 (10) A, b = 9.119 (7) A, c = 8.599 (7) Á, a = 66.81 (2)°, ß = 99.94 (3)°, y = 107.08 (2)°. Observed and calculated (Z = 2) densities are 1.60 (4) and 1.63 g/cm3, respectively. Least-squares refinement, based upon 1363 independent nonzero counter data, converged to a conventional discrepancy factor of 0.036. The binuclear structure contains two tricarbonyliron groups linked by bridging N=C(CH3)2 and ON=C(CH3)z ligands and by an iron-iron bond of length 2.484 (2) Á. The 2-propanoximato ligand bridges diatomically, forming a novel Fe-N-O-Fe linkage. Relatively little perturbation of the orientations of the Fe(CO)3 groups or of the iron coordination spheres is observed, despite the presence of both monatomic and diatomic bridging ligands. Distances and angles within the ON=C(CH3)2 group are consistent with the presence of a C=N double bond (1.291 (7) Á) and a N-0 single bond (1.351 (6) Á). The Fe-N distances range in length from 1.902 (4) to 1.982 (5) A, with the shorter distances involving the monatomically bridging isopropylidenamido ligand. The Fe-0 bond length is 1.952 (4) A.

show abstract

Organonitrogen derivatives of metal carbonyls. VI. Novel products reactions of 2-bromo-2-nitrosopropane with metal carbonylanions

Cited by 44 publications

References 23 publications

New Catalytic Properties of Iron Porphyrins: Model Systems for Cytochrome P450-Catalyzed Dehydration of Aldoximes

New Catalytic Properties of Iron Porphyrins: Model Systems for Cytochrome P450-Catalyzed Dehydration of Aldoximes

The First Acetimine Gold(I) and Gold(III) Complexes and the First Acetonine Complexes

Crystal and molecular structure of a bis(tricarbonyliron) complex containing bridging isopropylidenamido and 2-propanoximato(O, N) ligands

Contact Info

Product

Resources

About