Detection of aryllead(IV) carboxylates and their solvent adducts by ESI-mass spectrometry

Aplin, Robin T.; Buston, Jonathan Ε. H.; Moloney, Mark G.

doi:10.1016/s0022-328x(01)01329-8

Cited by 8 publications

(10 citation statements)

References 18 publications

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“…Similar results have been observed for Me 3 PbOAc [5]. Aryllead(IV) carboxylates have also been studied [27] and ESI has been used in the 'bare metal' or 'elemental' mode, for the quantitative analysis of organolead compounds [28]. A study of diphenyl lead(IV) thiosemicarbazonate complexes found that fragmentation by loss of two phenyl groups occurred first, giving product ions in which the Pb-S bond is retained [29].…”

Section: Resultssupporting

confidence: 61%

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Pham¹,

Henderson²,

Nicholson³

et al. 2007

Journal of Organometallic Chemistry

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Reactions of [Pt 2 (l-S) 2 (PPh 3 ) 4 ] with Ph 3 PbCl, Ph 2 PbI 2 , Ph 2 PbBr 2 and Me 3 PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + (R 3 = Ph 3 , Ph 2 I, Ph 2 Br, Me 3 ) isolated as PF 6 À or BPh 4 À salts. In the case of the Me 3 Pb and Et 3 Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt 2 (l-S)(l-SR)(PPh 3 ) 4 ] + (R = Me, Et). X-ray structure determinations on [Pt 2 (l-S) 2 (PPh 3 ) 4 PbMe 3 ]PF 6 and [Pt 2 (l-S) 2 (PPh 3 ) 4 PbPh 2 I]PF 6 have been carried out, revealing different coordination modes. In the Me 3 Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph 2 PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt 2 S 2 } metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh 3 in all cases; for R = Ph, loss of PbPh 2 occurs, yielding [Pt 2 (l-S) 2 (PPh 3 ) 3 Ph] + , while for R = Me, reductive elimination of ethane gives [Pt 2 (l-S) 2 (PPh 3 ) 3 PbMe] + , which is followed by loss of CH 4 .

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Section: Resultssupporting

confidence: 61%

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Pham¹,

Henderson²,

Nicholson³

et al. 2007

Journal of Organometallic Chemistry

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“…As a contribution to knowledge about lead(IV) complexes, we have studied the complexes formed by Pb(C 6 H 5 ) 2 (OAc) 2 with salicylaldehyde, 2‐ketobutyric acid, pyridine‐2‐carbaldehyde, 2‐acetylpyridine, and 2‐benzoylpyridine thiosemicarbazones (H 2 STSC, H 2 MePATSC, HPyTSC, HAcPyTSC, and HBPyTSC, see Table 1), in solution in MeOH, by ESI‐MS. Although some previous work has been done using ESI for the analysis of organolead(IV) compounds,14–16 and several derivatives containing diorganolead(IV) and thiosemicarbazone moieties have been prepared,17–20 the present report is, to the best of our knowledge, the first study of diorganolead thiosemicarbazonates by ESI‐MS. This work forms part of the search for chelating agents that can be used for effective chemotherapy of organolead poisoning.…”

Section: Parent Thiosemicarbazones Used To Prepare Complexes 1–6mentioning

confidence: 98%

Electrospray ionization mass spectrometry in the structural characterization of some diphenyllead(IV) thiosemicarbazonates

Casas¹,

García‐Tasende²,

Sordo³

et al. 2004

Rapid Comm Mass Spectrometry

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The behavior in electrospray ionization mass spectrometry (ESI-MS) conditions of some complexes formed by Pb(C6H5)2(OAc)2 with salicylaldehyde, 2-ketobutyric acid, pyridine-2-carbaldehyde, 2-acetylpyridine, and 2-benzoylpyridine thiosemicarbazones, was studied in detail with the aid of collisional experiments performed by ion trap. The homoleptic complexes of tridentate thiosemicarbazonate dianions (TSC2-) lose the phenyl groups first, destabilizing the high oxidation state of the metal and leading to Pb(II) complexes in which the TSC2- ligand or a part of it remains coordinated to the metal. The main difference among the complexes derives from the presence of a carboxylate group on the 2-ketobutyric acid thiosemicarbazonato ligand, which probably interacts with a Na+ cation leading to ESI-generated [M+Na]+ species. In the absence of the carboxylate group, the production of abundant protonated molecules is observed. These different behaviors have been rationalized from the structural point of view. The heteroleptic mononuclear complexes, including thiosemicarbazonate and AcO- monoanions in the coordination sphere, do not yield intact ionized molecular species, and the most abundant ESI-generated ion is due to AcO- loss. The spectrum of the binuclear heteroleptic complex formed by the salicylaldehyde thiosemicarbazonate monoanion is conditioned by the weak bonding interaction displayed by the acetate bridge. MSn experiments yield important information on the relative ligand-Pb bond strengths. This work forms part of the search for chelating agents that can be used for effective chemotherapy of organolead poisoning.

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“…As (Florencio et al, 1997) Co (Alsberg et al, 2001) Fe (Bakhtiar & Kaifer, 1998;KaneMaguire et al, 1996;Murao et al, 2005;Quirke & Van Berkel, 2001;Tharamani et al, 2008) Ge (Lamb & Sweetman, 1996) Ir (Ogo et al, 1999) Ge, Ni (Goicoechea & Sevov, 2006b) Mo (Thompson et al, 2003) Os (Dyson et al, 2000) Pb (Aplin et al, 2002) Ru (Kriesel et al, 1998;Pelagatti et al, 2005) Sb (Lintschinger et al, 1998) (Continued)…”

Section: A Basic Ionization Mechanisms Of Organometallic Compoundsmentioning

confidence: 99%

“…As (Florencio et al, 1997); Au (Goss et al, 2003;Kilpin et al, 2007); Bi (Dostál et al, 2009b;Chovancová et al, 2009); Fe (Alley & Henderson, 2001;Henderson & Alley, 2002;Pla-Quintana & Roglans, 2005); Ge (Jirásko et al, 2009); Hg (Nicholson & Whitley, 2004); Pb (Aplin et al, 2002;Casas et al, 2004); Pd (Chevrin et al, 2007;Pla-Quintana & Roglans, 2005); Pt (Hartnell & Arnold, 2004); Ru (Ang et al, 2006;Pelagatti et al, 2005); Sb (Dostál et al, 2008;Dostál et al, 2009b;Chovancová et al, 2009);…”

Section: Z=na K LI Agmentioning

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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Detection of aryllead(IV) carboxylates and their solvent adducts by ESI-mass spectrometry

Cited by 8 publications

References 18 publications

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Tuning the sulfur–heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Electrospray ionization mass spectrometry in the structural characterization of some diphenyllead(IV) thiosemicarbazonates

Structural analysis of organometallic compounds with soft ionization mass spectrometry

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