The hydrogenphosphate complex of (1,5-cyclooctadiene)iridium(I), {[Bu4N][(1,5-COD)Ir·HPO4]}n: synthesis, spectroscopic characterization, and ES-MS of a new, preferred precursor to HPO42− and Bu4N+ stabilized Ir(0)n nanoclusters

Özkâr, Saim; Finke, Richard G.

doi:10.1016/j.jorganchem.2003.10.038

Cited by 11 publications

(18 citation statements)

References 26 publications

(38 reference statements)

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“…Characterization of the isolated complex included 1 H, 13 C, and 31 P NMR, elemental analysis, and electrospray ionization mass spectrometry (ESI-MS) that provided suggestive, albeit not definitive evidence, that m = 2. Hence, the more general m -based formulation was reported previously, {[(1,5-COD)Ir I ·HPO 4 ] m } m − . ,, Noteworthy and as cited in the 2004 study, the O–O distance in HPO 4 2– is expected to be ca. 2.5 Å, whereas a single Ir bound to a bidentate oxo ligand such as HPO 4 2– requires an O–O distance between 2.8 and 3.3 Å (depending on the Ir–O distance) .…”

Section: Introductionmentioning

confidence: 84%

“…Previous studies from our lab reported that HPO 4 2– can serve as an effective stabilizer for Ir(0) n nanoparticles formed from the isolated complex, ,, {[(1,5-COD)Ir I ·HPO 4 ] m } m − . Characterization of the isolated complex included 1 H, 13 C, and 31 P NMR, elemental analysis, and electrospray ionization mass spectrometry (ESI-MS) that provided suggestive, albeit not definitive evidence, that m = 2.…”

Section: Introductionmentioning

confidence: 97%

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Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–

2019

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Following a summary of the relevant literature on nucleation and applicable nucleation and growth models and mechanisms, the kinetics and molecular mechanism of nucleation are investigated in detail starting from [(1,5-COD)IrI(NCCH3)2][BF4], 1, which upon addition of HPO4 2– to 1 forms a neutral, phosphate-bridged species, {[(1,5-COD)IrI(NCCH3)]2·HPO4}0, 2, en route to {[(1,5-COD)IrI·HPO4]2[Bu4N]2}, 3. Post a list of the seven advantages of the {[(1,5-COD)IrI·HPO4]2}2– precatalyst as a novel bimetallic precursor for kinetic and mechanistic studies of nucleation, six important, previously unanswered questions are raised about the ill-understood but exceedingly broad and important topic of nucleation. 1H NMR solution speciation and Signer apparatus solution molecular weight studies establish that in situ prepared {[(1,5-COD)IrI·HPO4]2}2–, 3, exists predominantly in its indicated, dimeric form. The NMR studies also identify {[(1,5-COD)IrI(NCCH3)]2·HPO4}0, 2, as an important, metastable species with one less HPO4 2–, formed in a dissociative equilibrium of 3 to 2 plus HPO4 2–. Kinetic studies reveal a first-order dependence of nucleation on the concentration of 3 and hence rule out the higher-order dependence implied by classical nucleation theory. Additional kinetic studies reveal a telling, inverse, quadratic dependence on added HPO4 2–, results that unveil the previously unavailable insights that a simple bimetallic, Ir2 precursor is sufficient to enable low-molecularity nucleation via {[(1,5-COD)IrI(NCCH3)]2·HPO4}0, 2, as a kinetically competent intermediate, a unique example of a nucleation mechanism known in molecular detail from a precisely defined molecular precursor that also includes spectroscopic detection of a kinetically competent intermediate. The results with {[(1,5-COD)IrI·HPO 4 ]2}2– in comparison to previous results with {[(1,5-COD)IrI·POM]}8– (POM = the polyoxometalate P2W15Nb3O62 9–) allow insights into the details of nucleation, notably that Ir2 versus Ir3 kinetically effective nuclei are controlled by the different HPO 4 2– and POM 8– anion’s surface charge and resultant 2 versus 3 IrI(1,5-COD)+ moieties they are able to bind to achieve surface-charge neutrality. The state-of-the-art nucleation results allow a total of nine insights, conclusions, and two new working hypotheses, insights that promise to help drive a deeper understanding of nucleation, not just in transition-metal nanoparticle formation but hopefully more broadly across nature.

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Section: Introductionmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 97%

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–

2019

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“…Somewhat hidden behind the success of the Ir(0) n systems is the amount of synthesis and characterization of the first generation {(1,5-COD)Ir I ÁPOM} 8À precursor 81,82 and then the second-generation {[(1,5-COD)Ir I ÁHPO 4 ] 2 } 2À precursor 32,96,97 characterization of their nanoparticle products by as many…”

Section: Reviewmentioning

confidence: 99%

Particle formation mechanisms supported by in situ synchrotron XAFS and SAXS studies: a review of metal, metal-oxide, semiconductor and selected other nanoparticle formation reactions

Whitehead

Finke

2021

Mater. Adv.

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“…Ag (Rais et al, 2002) As (Pedersen & Francesconi, 2000) Au (Dinger & Henderson, 1998a, b;Dinger et al, 1998;Dinger & Henderson, 1999;Goss et al, 2003;Kilpin et al, 2007) Cu (Lipshutz et al, 1999) Fe (Alley & Henderson, 2001;Henderson & Alley, 2002) Hg (Nicholson & Whitley, 2004) Ir (Ozkar & Finke, 2004) Pb (Mester & Pawliszyn, 1999;Pham et al, 2007) Pd (Chevrin et al, 2007;Moreno-Manas et al, 2003;Pla-Quintana & Roglans, 2005) Pt (Mastrorilli et al, 2004) Re (Jiang et al, 2000) Ru (Wang et al, 2002;Yeo et al, 1999) Sb (Brown et al, 2006) Sn (Beckmann et al, 2002;Henderson & Taylor, 1996;Lawson et al, 1996;Yeo et al, 2001) Te (Beckmann et al, 2005) ESI QqQ…”

Section: A Basic Ionization Mechanisms Of Organometallic Compoundsmentioning

confidence: 99%

Structural analysis of organometallic compounds with soft ionization mass spectrometry

Jirásko

Holčapek

2010

Mass Spectrometry Reviews

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The analysis of organometallic compounds with mass spectrometry has some special features in comparison with organic and bioorganic compounds. The first step is the choice of a suitable ionization technique, where the electrospray ionization is certainly the best possibility for most classes of organometallic compounds and metal complexes. Some ionization mechanisms of organometallic compounds are comparable to organic molecules, such as protonation/deprotonation, and adduct formation with sodium or potassium ions; however, in many cases, different mechanisms and their combinations complicate the spectra interpretation. Organometallics frequently undergo various types of adduct and polymerization reactions that result in significantly higher masses observed in the spectra in comparison to molecular weights of studied compounds. Metal elements typically have more natural isotopes than common organic elements, which cause characteristic wide distributions of isotopic peaks; for example, tin has ten natural isotopes. The isotopic pattern can be used for the identification of the type and number of metal elements in particular ions. The ionization and fragmentation behavior also depend on the type of metal atom; therefore, our discussion of mass spectra interpretation is divided according to the different type of organometallic compounds. Among various types of mass spectrometers available on the market, trap-based analyzers (linear or spherical ion-traps, Orbitrap) are suitable to study complex fragmentation pathways of organometallic ions and their adducts, whereas high-resolution and high-mass accuracy analyzers (time-of-flight-based analyzers, or Fourier transform-based analyzers-Orbitrap or ion cyclotron resonance mass spectrometers) provide accurate masses applicable for the determination of the elemental composition of individual ions.

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The hydrogenphosphate complex of (1,5-cyclooctadiene)iridium(I), {[Bu4N][(1,5-COD)Ir·HPO4]}n: synthesis, spectroscopic characterization, and ES-MS of a new, preferred precursor to HPO42− and Bu4N+ stabilized Ir(0)n nanoclusters

Cited by 11 publications

References 26 publications

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–

Particle formation mechanisms supported by in situ synchrotron XAFS and SAXS studies: a review of metal, metal-oxide, semiconductor and selected other nanoparticle formation reactions

Structural analysis of organometallic compounds with soft ionization mass spectrometry

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The hydrogenphosphate complex of (1,5-cyclooctadiene)iridium(I), {[Bu4N][(1,5-COD)Ir·HPO4]}n: synthesis, spectroscopic characterization, and ES-MS of a new, preferred precursor to HPO42− and Bu4N+ stabilized Ir(0)n nanoclusters

Cited by 11 publications

References 26 publications

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)IrI·HPO4]2}2–

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)IrI·HPO4]2}2–

Particle formation mechanisms supported by in situ synchrotron XAFS and SAXS studies: a review of metal, metal-oxide, semiconductor and selected other nanoparticle formation reactions

Structural analysis of organometallic compounds with soft ionization mass spectrometry

Contact Info

Product

Resources

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Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–

Nucleation Kinetics and Molecular Mechanism in Transition-Metal Nanoparticle Formation: The Intriguing, Informative Case of a Bimetallic Precursor, {[(1,5-COD)Ir^I·HPO₄]₂}^2–