Dibenzylmercury

Hitchcock, Peter B.

doi:10.1107/s0567740879004647

Cited by 11 publications

(3 citation statements)

References 7 publications

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“…In crystals of dibenzylmercury the monomers are arranged in chains with Hg- - -Hg contacts of 3.54 Å ( 7 ). This feature was not commented on by the authors but recognized in later studies . The distance coincides perfectly with the proposed sum of the van der Waals radii (above).…”

Section: Mercurophilicitysupporting

confidence: 86%

Mercurophilic Interactions

Schmidbaur

Schier

2015

Organometallics

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The widely confirmed abundance of aurophilic interactions in the structural chemistry of gold(I) compounds gives reason to scrutinize the evidence for analogous mercurophilic interactions in mercury(II) compounds more sporadically advanced in the literature. From the inventory of early observations and more recently accumulated data it appears that the equilibrium distances of intra-and intermolecular Hg---Hg contacts (ca. 3.5 Å) are generally much larger than those of Au---Au contacts (ca. 3.0 Å). There are very few estimations of the small energy contributions associated with the Hg---Hg contacts from experimental data, but quantumchemical calculations have confirmed that these energies also are generally much lower than those for the Au---Au contacts. Notwithstanding, there are several special cases where particularly short Hg---Hg distances, or the preferred modes of associations of molecules into oligo-or polymeric arrays, do indicate significant attractive mercurophilic interactions. Photophysical phenomena also suggest that for several groups of oligomeric organomercury(II) compounds there is a much stronger Hg−Hg interaction in the excited state, with interesting consequences for the emissive properties. Interestingly, the most intriguing observations that suggest mercurophilic interactions, like the polymercuration of oxygen, nitrogen, and carbon, date back to the 19th century (Roucher in 1844, Millon in 1839, Sakurai in 1880, and Hofmann in 1900, respectively) and still call for a rationalization.

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Section: Mercurophilicitysupporting

confidence: 86%

Mercurophilic Interactions

Schmidbaur

Schier

2015

Organometallics

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“…The Pt−Si bond length in 20a is 2.337(3) Å and is the first Pt(IV)−Si distance to be determined. The Pt− Si bond length is similar to those seen for R 3 Si ligands trans to halides in platinum(II) complexes; the Pt−Si bond lengths are 2.317(2) Å for (+)- trans -[PtCl{SiMe(1-C 10 H 7 )Ph}(PMe 2 Ph) 2 ] and 2.330(17) Å for trans -[PtBr(Me 3 Si)OPEt 3 ) 2 ] …”

Section: Resultssupporting

confidence: 60%

Synthesis and Characterization of Group 14−Platinum(IV) Complexes

1996

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The reactions of group 14 compounds Me n EX4-n (E = Si, Ge, Sn; X = Cl, Br, I) with electron-rich [PtMe2(diimine)] complexes give facile trans oxidative addition of the E−X bond (E = Si, X = Br, I; E = Ge, Sn, X = Cl, Br, I). The oxidative additions occur more readily for Me n EX4-n in the sequences X = I > Br > Cl and E = Sn > Ge > Si. The first stable silylplatinum(IV) complexes have been prepared in this way, and the X-ray crystal structure of [PtIMe2(Me3Si)(bpy)] shows an exceptionally long Pt−I bond length (2.963(1) Å) consistent with the high trans influence of the trimethylsilyl group. 1H NMR studies show that the oxidative addition involving germanium and tin reagents is easily reversible. Several of the platinum(IV)−tin complexes have a second molecule of tin reagent incorporated into the crystal lattice. The X-ray crystal structure of [PtIMe2(Me3Sn)(bpy- t bu2)]2·Me3SnI· CH2Cl2 shows two distinct complexes (1:1 ratio) to be present in the unit cell. The first is the product of trans oxidative addition, [PtIMe2(Me3Sn)(bpy- t bu2)], and the second is [PtIMe2(Me3Sn)(bpy− t bu2)]·Me3SnI. In this second complex the platinum-bound iodo ligand coordinates to the tin center of the Me3SnI molecule to give a trigonal-bipyramidal tin center.

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“…Hg 3 ( o ‐C 6 F 4 ) 3 (arene) 16 or Hg(C 6 F 5 ) 2 (arene) 17} and inter‐ or intramolecular contacts between mercury and arene rings of aryl substituents in organometallic [e.g. Hg(CH 2 Ph) 2 18a or HgDmp 2 18b) or coordination compounds (e.g. weak intermolecular coordination in mercury triazenides: [11, 12]) with typical Hg···C distances in the range 3.15–3.50 Å.…”

Section: Resultsmentioning

confidence: 99%

Halogenomercury Salts of Sterically Crowded Triazenides – Convenient Starting Materials for Redox‐Transmetallation Reactions

Hauber

Seo

Niemeyer

2010

Zeitschrift anorg allge chemie

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Diaryl‐substituted triazenides Ar(Ar′)N3HgX [Ar/Ar′ = Dmp/Mph, X = Cl (2a), Br (3a), I (4a); Ar/Ar′ = Dmp/Tph, X = Cl (2b), I (4b) with Mph = 2‐MesC6H4, Mes = 2,4,6‐Me3C6H2, Tph = 2′,4′,6′‐triisopropylbiphenyl‐2‐yl and Dmp = 2,6‐Mes2C6H3] were synthesized by salt‐metathesis reactions in ethyl ether from the readily available starting materials Ar(Ar′)N3Li and HgX2. These compounds may be used for redox‐transmetallation reactions with rare‐earth or alkaline earth metals. Thus, reaction of 4b or 2b with magnesium or ytterbium in tetrahydrofuran afforded the triazenides Dmp(Tph)N3MX(thf) (5b: M = Mg, X = I; 6b: M = Yb, X = Cl) in good yield. All new compounds were characterized by melting point, 1H and 13C NMR spectroscopy and for selected species by IR spectroscopy or mass spectrometry. In addition, the solid‐state structures of triazenides 2a, 2b, 3a, 4b, 5b and 6b were investigated by single‐crystal X‐ray diffraction.

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Dibenzylmercury

Cited by 11 publications

References 7 publications

Mercurophilic Interactions

Mercurophilic Interactions

Synthesis and Characterization of Group 14−Platinum(IV) Complexes

Halogenomercury Salts of Sterically Crowded Triazenides – Convenient Starting Materials for Redox‐Transmetallation Reactions

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