Chip Nataro

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Papers by Chip Nataro

Synthesis, Structure, and Electrochemistry of an Electron-Rich Chiral Diaminoferrocene, (S,S)-Bis(2,5-dimethylpyrrolidinyl)ferrocene

Organometallics, 2005

The chiral diamine (S,S)-bis(2,5-dimethylpyrrolidinyl)ferrocene ( ) was prepared from diaminoferr... more The chiral diamine (S,S)-bis(2,5-dimethylpyrrolidinyl)ferrocene ( ) was prepared from diaminoferrocene and (2R,5R)-2,5-hexanediol cyclic sulfate in the presence of a base. The short C-N bond, long Fe-C(N) bond, and planar nitrogen observed in the crystal structure of 6 are consistent with efficient N-to-Cp electron donation. The resulting electron-rich metal center (with the most negative shift in redox potential yet observed for aminoferrocenes) was characterized electrochemically.

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Electrochemistry of Ru2Cp′2(CO)4 and Ru2Cp2(CO)3(PMe3) and the estimation of Ru2(μ-H) bond dissociation enthalpies

Journal of Organometallic Chemistry, 2002

The oxidation potentials for a series of diruthenium compounds have been measured. The heat of pr... more The oxidation potentials for a series of diruthenium compounds have been measured. The heat of protonation (−ΔHMHM) and oxidation potentials (E1/2) for a series of Ru2Cp′2(CO)4 (Cp′=Cp2, Cp*2, C5H4CH2C5H4, (C5H4CH2)2, (C9H7)2, C10H8, (HBpz3)2) compounds and Ru2Cp2(CO)3(PMe3) were used to estimate the homolytic RuHRu bond dissociation enthalpy (BDEs) using a thermochemical cycle. Poor correlation between −ΔHMHM and E1/2 was observed, as

Electrochemistry of P(CH2Fc)3 and derivatives

Journal of Organometallic Chemistry, 2011

The oxidative electrochemistry of P(CH2Fc)3 and three of its derivatives was examined. The electr... more

Lewis Acid-Base, Molecular Modeling, and Isotopic Labeling in a Sophomore Inorganic Chemistry Laboratory

Journal of Chemical Education, 2004

1-Methyl-1-Vinyl-3,3,5,5-Tetraphenylcyclotrisiloxane: An Organofunctional Cyclotrisiloxane

Journal of Inorganic and Organometallic Polymers and Materials, 2009

The characterization of 1-methyl-1-vinyl-3,3,5,5-tetraphenylcyclotrisiloxane by NMR(1H,13C,29Si) ... more The characterization of 1-methyl-1-vinyl-3,3,5,5-tetraphenylcyclotrisiloxane by NMR(1H,13C,29Si) and X-ray crystallography is reported. The central siloxane ring is planar with Si–O bond lengths and angles which are similar to those found in the structures of other cyclotrisiloxanes. There is significant thermal motion of the methyl and vinyl groups. Very low incorporation of the siloxane is observed in the radical catalyzed copolymerization of the siloxane with styrene.

Synthesis, Characterization, and Electrochemistry of Compounds Containing 1-Diphenylphosphino-1′-(di- tert -butylphosphino)ferrocene (dppdtbpf)

Organometallics, 2009

ABSTRACT The anodic electrochemistry of 1-di-tert-butylphosphino-1′-diphenylphosphinoferrocene (d... more ABSTRACT The anodic electrochemistry of 1-di-tert-butylphosphino-1′-diphenylphosphinoferrocene (dppdtbpf) was performed in methylene chloride with tetrabutlylammonium hexafluorophosphate as the supporting electrolyte. The electrochemistry is complicated by a chemical reaction after the oxidation. Three new transition metal complexes of dppdtbpf ([NiCl2(dppdtbpf)], [PtCl2(dppdtbpf)], and [Au2Cl2(dppdtbpf)]) were prepared and characterized. The electrochemistry of the three new compounds and one previously prepared compound ([PdCl2(dppdtbpf)]) was examined. In addition, the reaction of dppdtbpf with sulfur and/or selenium afforded a series of compounds containing a phosphine sulfide (dppSdtbpSf or dppdtbpSf), a phosphine selenide (dppSedtbpSef or dppdtbpSef), or both a phosphine sulfide and a phosphine selenide (dppSedtbpSf or dppSdtbpSef). These compounds were characterized by NMR, and the structures of three of the compounds were determined. Two of the structures are of the isomeric compounds, dppSdtbpSef and dppSedtbpSf, in which the sulfur and selenium atoms are switched between the two different phosphine groups. The anodic electrochemistry of these sulfur- and/or selenium-containing compounds was examined in methylene chloride. The potentials at which oxidation occurs are more positive than those of the free phosphine. Nearly all of the oxidations are complicated by at least one chemical reaction.

Analysis of 2-ferrocenylethanol by NMR, cyclic voltammetry and X-ray crystallography

Polyhedron, 1999

Ferrocenylethanol has been prepared and characterized by H and C NMR, cyclic voltammetry and X-ra... more Ferrocenylethanol has been prepared and characterized by H and C NMR, cyclic voltammetry and X-ray crystallography. The electrochemical data were compared to ferrocene and related compounds. The lattice constants for ferrocenylethanol (C H FeO) are 12 14 ā517.291(2) A and a5118.590(0)8. The crystal exists in R3 and there are six formula units per rhombohedral unit cell.

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Analysis of phosphines functionalized with crown ether groups by NMR and cyclic voltammetry

Polyhedron, 2001

The compound benzo-3,4-[18-crown-6]-diphenylphosphine was characterized by 31 P, 13 C and 1 H NMR... more The compound benzo-3,4-[18-crown-6]-diphenylphosphine was characterized by 31 P, 13 C and 1 H NMR in CDCl 3 and CD 3 CN and by cyclic voltammetry in CH 2 Cl 2 and CH 3 CN. The phosphine crown ether was found to be similar to triphenylphosphine in electrochemical and spectroscopic properties. Addition of M + PF 6 -(M + = Li + , Na + , or K + ) to the samples resulted in minimal changes in the observed 31 P spectra but significant differences in the electrochemistry. This suggests that binding a metal cation to the crown ether can be monitored electrochemically.

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BoPhoz Ligands: Anodic Electrochemistry and Complexes

Organometallics, 2005

The oxidative electrochemistries of two chiral metallocene phosphine-aminophosphine (BoPhoz) liga... more The oxidative electrochemistries of two chiral metallocene phosphine-aminophosphine (BoPhoz) ligands, R-Methyl BoPhoz ((R)-N-diphenylphosphino-N-methyl-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine) and R-Pcyco BoPhoz ((R)-N-dicyclohexylphosphino-N-methyl-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine)), were examined in methylene chloride. In addition the platinum(II) and palladium(II) complexes with a general formula [MCl 2 (P-P)] (M ) Pd or Pt; P-P ) R-Methyl BoPhoz or R-Pcyco BoPhoz) were prepared and characterized by NMR and cyclic voltammetry; the X-ray structures of the palladium complexes are reported.

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Electrochemistry of Late Transition Metal Complexes Containing the Ligand 1,1‘-Bis(diisopropylphosphino)ferrocene (dippf)

Organometallics, 2003

The chemically reversible oxidation of 1,1′-bis(diisopropylphosphino)ferrocene (dippf) was invest... more The chemically reversible oxidation of 1,1′-bis(diisopropylphosphino)ferrocene (dippf) was investigated using cyclic voltammetry. In addition, seven new compounds with general formulas of ) have been prepared. The Ni and Co compounds were found to be paramagnetic, and the Evans method was used to determine the magnetic moment for these compounds. The remaining compounds were characterized by 1 H, 13 C, and 31 P NMR. As an additional means of characterization, the molecular structures of [PtCl 2 (dippf)] and [ZnCl 2 (dippf)] were determined. The electrochemistry of the new compounds and the previously synthesized [PdCl 2 (dippf)] was investigated using cyclic voltammetry. The results of this investigation show that coordination of the dippf ligands leads to more positive oxidation potentials for the ferrocene backbone.

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Anodic Electrochemistry of Free and Coordinated 1,1‘-Bis(di-tert-butylphosphino)ferrocene

Organometallics

The electrochemistry of 1,1′-bis(di-tert-butylphosphino)ferrocene (dtbpf) was examined in methyle... more The electrochemistry of 1,1′-bis(di-tert-butylphosphino)ferrocene (dtbpf) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Two new complexes in which dtbpf was bound to a transition metal were prepared and characterized. The two new complexes as well as two previously reported complexes were analyzed by cyclic voltammetry. In addition, the chalcogenids, dtbpfS 2 and dtbpfSe 2 , were prepared and characterized by NMR and the structure of dtbpfSe 2 was determined. The oxidation of dtbpfS 2 is a simple one-electron process due to the presence of the iron center. In contrast, the oxidation of dtbpfSe 2 is electrochemically irreversible and appears to proceed by an EE mechanism. Chemical oxidation of dtbpfSe 2 resulted in the formation of [dtbpfSe 2 ][BF 4 ] 2 , in which a Se-Se bond formed. This compound was characterized by 31 P NMR and X-ray crystallography. A detailed analysis of the electrochemistry suggests that the oxidation of dtbpfSe 2 occurs by two separate one-electron processes. In addition, formation of the Se-Se bond was reversible.

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Electrochemistry of Group VI Metal Carbonyl Compounds Containing 1,1‘Bis(diphenylphosphino)ferrocene

Organometallics, 2004

The oxidative electrochemistry of a variety of homo-and bimetallic group VI metal carbonyl compou... more The oxidative electrochemistry of a variety of homo-and bimetallic group VI metal carbonyl compounds containing 1,1′-bis(diphenylphosphino)ferrocene (dppf) with the general formulas M(CO) 5 (dppf) (1a-c), M(CO) 4 (dppf) (2a-c), and (CO) 5 M(dppf)M′(CO) 5 (3a-f) (M, M′ ) Cr, Mo, W) was investigated. The effect of the group VI metal and the coordination mode of the dppf ligand on the potential at which the oxidation of the group VI metals and the ferrocene backbone of dppf occurred was examined.

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Ruthenium cluster compounds containing 1,1′-bis(diphenylphosphino)ferrocene (dppf): an electrochemical analysis and the crystal structure of [Ru3(CO)11]2(μ-dppf)

Journal of Organometallic Chemistry, 2003

... The assignment of the carbons was based upon the coupling constants and DEPT data. The 13 C--... more

Group 10 metal compounds of 1,1′-bis(diphenylphosphino)ferrocene (dppf) and 1,1′-bis(diphenylphosphino)ruthenocene: a structural and electrochemical investigation. X-ray structures of [MCl2(dppr)] (M=Ni, Pd)

Journal of Organometallic Chemistry, 2003

The oxidative electrochemistry of 1,1?-bis(diphenylphosphino)ferrocene (dppf) and 1,1?-bis(diphen... more The oxidative electrochemistry of 1,1?-bis(diphenylphosphino)ferrocene (dppf) and 1,1?-bis(diphenylphosphino)ruthenocene (dppr) was investigated at a variety of temperatures and concentrations. In addition, the oxidative electrochemistry of [NiCl 2 (dppf)] and [MCl 2 (dppr)] (M 0/Ni, Pd or Pt) compounds was studied. During the preparation of the dppr compounds, crystals of [NiCl 2 (dppr)] and [(PdCl 2 (dppr)] ×/CH 2 Cl 2 were obtained and the structures were determined. With the previously determined structures of [MCl 2 (dppf)] (M 0/Ni, Pd or Pt) and [PtCl 2 (dppr)], a thorough examination of the binding of dppf and dppr to Group 10 metals was performed.

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Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

Journal of Organometallic Chemistry, 2004

A new chemical oxidant [N(4-C6H4Br)3][B(C6F5)4], was prepared and used to synthesize [Fe(C5H5)2][... more

Synthesis and electrochemistry of late transition metal complexes containing 1,1′-bis(dicyclohexylphosphino)ferrocene (dcpf). The X-ray structure of [PdCl2(dcpf)] and Buchwald–Hartwig catalysis using [PdCl2(bisphosphinometallocene)] precursors

Journal of Organometallic Chemistry, 2006

The electrochemistry of 1,1′-bis(dicyclohexylylphosphino)ferrocene (dcpf) was examined in methyle... more The electrochemistry of 1,1′-bis(dicyclohexylylphosphino)ferrocene (dcpf) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate or tetrabutylammonium tetrakis(pentafluorophenyl)borate as the supporting electrolyte. The oxidation of dcpf is complicated by a follow-up reaction. Seven new complexes containing dcpf and one new compound containing 1,1′-bis(di-tert-butylphosphino)ferrocene (dtbpf) were prepared and characterized. The new complexes were analyzed by cyclic voltammetry and the oxidation of these complexes

Derivatives of 1,1′-bis(diphenylphosphino)ferrocene (dppf): Electrochemistry, complexation and the X-ray structures of 1,1′-bis(diphenylphosphino)osmocene (dppo) and [PdCl2(dppo)]

Journal of Organometallic Chemistry, 2006

The oxidative electrochemistry of 1, 1′-bis (diphenylphosphino) osmocene (dppo) and 1, 1′-bis (di... more

Synthesis and characterization of 1-methyl-1-silaindane and 1-methyl-1-germaindane

by Chip Nataro and Donald Berry

Journal of Organometallic Chemistry, 2008

New synthetic routes to 1-methyl-1-silaindane (1b) and 1-methyl-1-germaindane (1b) were developed... more

Electrochemistry and complexation of Josiphos ligands

Journal of Organometallic Chemistry, 2007

The oxidative electrochemistry of 11 chiral bis-phosphinoferrocene ligands, all within the Josiph... more The oxidative electrochemistry of 11 chiral bis-phosphinoferrocene ligands, all within the Josiphos class of ligands, was examined in methylene chloride. The oxidation of these ligands displays multiple waves of varying chemical reversibility. Palladium(II) and platinum(II) complexes with the general formula [MCl2(P–P)] (M=Pd or Pt; P–P=Josiphos) were prepared, characterized by NMR and cyclic voltammetry. The electrochemistry simplifies greatly upon coordination of

Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

Journal of Organometallic Chemistry, 2011

The electrochemistry of 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate ([dppc][PF6]... more The electrochemistry of 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate ([dppc][PF6]), 1,1′-bis(dicyclohexylphosphino)cobaltocenium hexafluorophosphate ([dcpc][PF6]), 1,1′-bis(di-iso-propylphosphino)cobaltocenium hexafluorophosphate ([dippc][PF6]), and 1-(di-tert-butylphosphino)cobaltocenium hexafluorophosphate ([1-dtbpc][PF6]) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. A reversible reductive wave followed by an irreversible wave at more negative potentials was observed. Ten new phosphinothioyl ([dppcS2][PF6], [dcpcS2][PF6], [dippcS2][PF6], [1-dtbpcS][PF6], and 1,1′-bis(dicyclohexylphosphinothioyl)ferrocene) and phosphinoselenoyl derivatives ([dppcSe2][PF6], [dcpcSe2][PF6], [dippcSe2][PF6], [1-dtbpcSe][PF6], and