Lead

Harrison, Philip G.

doi:10.1016/b978-008046519-7.00019-8

Cited by 15 publications

(10 citation statements)

References 91 publications

(37 reference statements)

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“…In contrast divalent organolead compounds are relatively rare and their chemistry is poorly explored. 298,299 The organoplumbylene chemistry has been restricted mostly around the first well-characterized organolead(II) compounds Pb(Z 5 -C 5 H 5 ) 2 and Pb[CH(SiMe 3 ) 2 ] 2 [302][303][304] But relatively little is known about the chemistry of smaller heteroleptic organoplumbylene derivatives, and studies in this area have been emerging in recent years. 296,[305][306][307] In 2009 we reported the preparation and characterization of a number of organoplumbylene compounds LPb(Me) (115), LPb(Ph) (116), and LPb(CCPh) (117).…”

Section: Organoplumbylenesmentioning

confidence: 99%

Interstellar molecules: guides for new chemistry

2010

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Interstellar space is among the most remarkable chemical laboratories in the universe. The existence of many unstable species with low-valent main group elements in the interstellar medium inspired us to investigate the feasibility of laboratory synthesis of such unstable molecules. Particularly the lighter Group 14 element carbon plays a very important role in space astrochemistry. Low-valent carbon as well as silicon were detected in the interstellar environment. This article describes our recent efforts in developing amazing chemistry of heavier low-valent Group 14 elements. This study unravels that the disproportionation pathway of the low-valent Group 14 elements can be arrested by using a sterically protected ligand, then one can artificially generate the situation observed in the interstellar surrounding where the chance of disproportionation is very low as the molecules are extremely dilute.

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Section: Organoplumbylenesmentioning

confidence: 99%

Interstellar molecules: guides for new chemistry

2010

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“…Organolead chemistry is primarily concerned with compounds of lead in the oxidation state IV. In contrast, the chemistry of Pb(II) tends to be dominated by compounds with inorganic ligands, and bivalent organolead compounds are relatively rare and their chemistry is poorly explored. , The first well-characterized organolead(II) species was the bent sandwich complex Pb(η 5 -C 5 H 5 ) 2 , and this has been supplemented by a number of related derivatives that have a variety of substituents at the cyclopentadienyl ring . For many years, however, Pb{CH(SiMe 3 ) 2 } 2 was the only stable σ-bonded organolead(II) compound .…”

Section: Introductionmentioning

confidence: 99%

Terphenyl Ligand Stabilized Lead(II) Derivatives of Simple Organic Groups: Characterization of Pb(R)C₆H₃-2,6-Trip₂(R = Me, t-Bu, or Ph; Trip = C₆H₂-2,4,6-i-Pr₃), {Pb(μ-Br)C₆H₃-2,6-Trip₂}₂, py·Pb(Br)C₆H₃-2,6-Trip₂(py = Pyridine), and the Bridged Plumbylyne Complex [{W(CO)₄}₂(μ-Br)(μ-PbC₆H₃-2,6-Trip₂)]

Twamley

Power

2000

Organometallics

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The reaction between 1 equiv of the sterically encumbered lithium terphenyl Et 2 O‚LiC 6 H 3 -2,6-Trip 2 and PbBr 2 in diethyl ether afforded the organolead(II) halide compound {Pb(µ-Br)C 6 H 3 -2,6-Trip 2 } 2 (1) as orange crystals. Treatment of 1 with a stoichiometric amount of pyridine (py) gave the complex py‚Pb(Br)C 6 H 3 -2,6-Trip 2 (2) as yellow needles. The addition of 1 equiv of methylmagnesium bromide, tert-butyllithium, or phenyllithium to 1 resulted in the diorganolead(II) compounds Pb(R)C 6 H 3 -2,6-Trip 2 (R ) Me, 3; t-Bu, 4; or Ph, 5) in good yield. The compounds 3 and 5 are the first stable, monomeric lead(II) derivatives involving the simplest alkyl and aryl groups Me and Ph. Reaction of 1 with W(CO) 5 THF did not yield the expected plumbylene complex (CO) 5 W{Pb(Br)C 6 H 3 -2,6-Trip 2 }. Instead, the bridged plumbylyne species [{W(CO) 4 } 2 (µ-Br)(µ-Pb-C 6 H 3 -2,6-Trip 2 )] ( 6) was obtained in low yield. All compounds were characterized by X-ray crystallography, 1 H and 13 C NMR, IR, and UV-vis spectroscopy. 207 Pb NMR spectra of 3-5 were also obtained. The results demonstrate the effectiveness of the terphenyl ligand in creating a protected cavity at a site in which normally unstable moieties are stabilized against decomposition reactions.

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“…Compounds that feature bonds between lead and the transition elements are less thoroughly investigated than their lighter group 14 element congeners . Lower-valent lead derivatives are particularly rare and are confined to a handful of derivatives of various kinds. , Examples include the spectroscopically characterized plumbylene complexes (CO) 5 MoPb{CH(SiMe 3 ) 2 } 2 and [Pd(η 3 -C 3 H 5 )(μ-Cl)Pb{N(SiMe 3 ) 2 } 2 ] 2 as well as the structurally characterized bismetalloplumbylene derivatives {(η 5 -C 5 H 5 )(CO) 3 Mo} 2 Pb·THF and [{(η 5 -C 5 H 5 )(CO) 3 Mo} 2 Pb] 2 (dimerized through weak isocarbonyl interactions), both of which feature three-coordinate Pb(II) centers …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of the Metalloplumbylenes (η⁵-C₅H₅)(CO)₃M-P̈b-C₆H₃-2,6-Trip₂(M = Cr, Mo, or W; Trip = −C₆H₂-2,4,6-i-Pr₃)

Power

Boltes

et al. 1999

Organometallics

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The reaction of Pb(Br)C6H3-2,6-Trip2 (Trip = C6H2-2,4,6-i-Pr3), generated in situ, with the salts Na[M(η5-C5H5)(CO)3]·DME (M = Cr, Mo, or W; DME = 1,2-dimethoxyethane) affords the novel green, crystalline metalloplumbylenes (η5-C5H5)(CO)3M-P̈b-C6H3-2,6-Trip2 (M = Cr, 1; Mo, 2; W, 3) in moderate yield. The compounds were characterized spectroscopically (1H, 13C, and 207Pb NMR, IR, and UV−vis) and by combustion analysis. In addition the X-ray crystal structures of 1−3 were determined. The compounds feature strongly bent geometries at lead (M−Pb−C = 108.6(2)−113.58(9)°) and relatively long M−Pb distances (2.9092(9) Å, Cr; 2.9845(7) Å, Mo; 2.9809(10) Å, 3.0055(6) Å W), which are consistent with single M−Pb bonding. The stability of the complexes, which melt with decomposition in the range 210−226 °C, is attributed to steric protection of the metal centers by the very large −C6H3-2,6-Trip2 substituent. The compounds are the first examples of metalloplumbylenes that feature a bent two-coordinate lead geometry.

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Lead

Cited by 15 publications

References 91 publications

Interstellar molecules: guides for new chemistry

Interstellar molecules: guides for new chemistry

Synthesis and Characterization of the Metalloplumbylenes (η⁵-C₅H₅)(CO)₃M-P̈b-C₆H₃-2,6-Trip₂(M = Cr, Mo, or W; Trip = −C₆H₂-2,4,6-i-Pr₃)

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Lead

Cited by 15 publications

References 91 publications

Interstellar molecules: guides for new chemistry

Interstellar molecules: guides for new chemistry

Synthesis and Characterization of the Metalloplumbylenes (η5-C5H5)(CO)3M-P̈b-C6H3-2,6-Trip2(M = Cr, Mo, or W; Trip = −C6H2-2,4,6-i-Pr3)

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Synthesis and Characterization of the Metalloplumbylenes (η⁵-C₅H₅)(CO)₃M-P̈b-C₆H₃-2,6-Trip₂(M = Cr, Mo, or W; Trip = −C₆H₂-2,4,6-i-Pr₃)