Coordination complexes of the bismuth(iii) thiolates Bi(SC6F5)3 and Bi(SC6Cl5)3 with pyridine ligands

Anderson, Kirsty M.; Baylies, Christian J.; Jahan, Afsana; Norman, Nicholas C.; Orpen, A. Guy; Starbuck, Jonathan

doi:10.1039/b305711a

Cited by 28 publications

(25 citation statements)

References 20 publications

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“…This is a unique structural feature within the small number of literature-known compounds BiR(SR 0 ) 2 (R, R 0 ¼ aryl, alkyl; for details see ESI †). [42][43][44][45]…”

Section: Resultsmentioning

confidence: 99%

Methylbismuth: an organometallic bismuthinidene biradical

et al. 2020

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“…This is a unique structural feature within the small number of literature-known compounds BiR(SR 0 ) 2 (R, R 0 ¼ aryl, alkyl; for details see ESI †). [42][43][44][45]…”

Section: Resultsmentioning

confidence: 99%

Methylbismuth: an organometallic bismuthinidene biradical

et al. 2020

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“…General considerations (9). Tmeda (0.099 g, 0.83 mmol) was added dropwise to a yellow slurry of 1 (0.200 g, 0.415 mmol) in toluene (3 mL).…”

Section: Methodsmentioning

confidence: 99%

“…Dalton Transactions solid-state NMR and DFT calculations. 207 Pb SSNMR spectra of [9][10][11] As][(PhS) 3 Pb] (12) were acquired in a piecewise fashion with the CP/CPMG pulse sequence. The WURST-CPMG pulse sequence was also used to obtain the ultra-wideline (UW) 207 Pb SSNMR spectra in a single experiment.…”

Section: Papermentioning

confidence: 99%

“…Heavy p-block metals, such as Pb(II), are potentially diverse coordination centers for such systems. [7][8][9][10][11][12][13] For example, the large atomic radius of Pb(II) allows high coordination numbers for the element, while the number of possible bonding environments is augmented by the variable stereochemical activity of its valence lone pair. 11,[13][14][15][16] The preference for high coordination numbers typically manifests itself in the formation of polymeric species, as is observed in the solid-state structures of the Pb(II) thiolates [(RS) 2 Pb] 4 (R = C 6 H 5 , 4-MeC 6 H 4 , CH 2 ) [17][18][19][20] via extensive intermolecular Pb⋯S interactions.…”

Section: Introductionmentioning

confidence: 99%

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Structural variation in ethylenediamine and -diphosphine adducts of (2,6-Me2C6H3S)2Pb: a single crystal X-ray diffraction and 207Pb solid-state NMR spectroscopy study

et al. 2013

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Coordination complexes of (2,6-Me2C6H3S)2Pb (1) with flexible bidentate ligands have been prepared to explore new bonding environments for Pb(II) thiolates. The reaction of 1 with a series of ethylenediamine and ethylenediphosphine ligands resulted in isolation of the adducts [(2,6-Me2C6H3S)2Pb]2(tmeda) (9), [(2,6-Me2C6H3S)2Pb]3(dmpe) (10) and [(2,6-Me2C6H3S)2Pb]2(dppe) (11) [tmeda = N,N,N',N'-tetramethylethylenediamine; dmpe = bis(dimethylphosphino)ethane; dppe = bis(diphenylphosphino)ethane]. The X-ray crystal structure of 9 shows a dinuclear species in which tmeda is chelating a ψ-trigonal bipyramidal S2N2 Pb centre via axial and equatorial sites. The structure of 10 displays a trinuclear structural unit in which dmpe is chelating a ψ-trigonal bipyramidal S2P2 Pb centre via equatorial sites. Compounds 9 and 10 also contain a second unique metal centre with ψ-tetrahedral S3Pb bonding motifs. The structure of 11 shows the dppe ligand bridging two Pb ψ-tetrahedral S2P metal bonding environments. Static (207)Pb solid-state NMR (SSNMR) spectra of 9-11 and [Ph4As][(PhS)3Pb] (12) were acquired with cross polarization (CP)-CPMG and frequency swept pulse (WURST)-CPMG pulse sequences, and the efficiencies of these pulse sequences are compared. The (207)Pb SSNMR spectra reveal that the lead chemical shift anisotropies (CSA) vary greatly between the different Pb sites, and are generally large in magnitude. DFT calculations are utilized to relate the orientations of the (207)Pb nuclear magnetic shielding tensors to the molecular structures, and to aid in spectral assignment where multiple Pb centres are present. The combination of X-ray diffraction, (207)Pb SSNMR and DFT is shown to be invaluable for the structural characterization of these important structural motifs, and should find wide-ranging application to numerous lead coordination compounds.

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“…Since thiols are acid compounds (hydrosulfuric acid derivatives), mercaptides can also be obtained by reacting them with organometallic compounds [Clegg et al, 1995;Anderson et al, 2003]:…”

Section: Mercaptide Preparationmentioning

confidence: 99%