Arsenic, Antimony and Bismuth
01 Jan 2021-pp 321-417
About: The article was published on 2021-01-01. It has received 5 citations till now. The article focuses on the topics: Bismuth & Antimony.
Citations
More filters
TL;DR: In this article , the ortho-bismuthination of hexaphenyl carbodiphosphorane enables a robust framework with geometrically constrained bismuth bonding interactions, which are highly tunable by cationization.
Abstract: Bismuth complexes stabilized by carbon-based donor ligands are underserved by their instability, often due to facile ligand dissociation and deleterious protonolysis. Herein, we show that the ortho-bismuthination of hexaphenylcarbodiphosphorane enables a robust framework with geometrically constrained carbone-bismuth bonding interactions, which are highly tunable by cationization. The carbodiphosphorane bismuth halides (1 and 2) are remarkably air-stable and feature unprecedented trans carboneC-Bi-X ligation, resulting in highly elongated Bi-X bonds. In contrast to known carbone-bismuth complexes, hydrolytic activation of the carbone yields well-defined organobismuth complexes, and subsequent dehydrohalogenation is feasible using potassium bis(trimethylsilyl)amide or N-heterocyclic carbenes. The redox-flexibility of this framework was evaluated in the high catalytic activity of 1 and 2 for silylation of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) under mild conditions (50 °C, 24-96 h) and low catalyst loadings (5-10 mol %), which suggests the accessibility of short-lived hydridic and radical bismuth species. The reaction of 1, PhSiH3, and tris(pentafluorophenyl)borane (BCF) yields the first crystallographically characterized bismuth hydridoborate complex as an ionic species (9), presumably by BCF-mediated hydride abstraction from an unobserved [Bi]-H intermediate. All isolated compounds have been characterized by heteronuclear NMR spectroscopy and X-ray crystallography, and the bonding situation in representative complexes (1, 2, 5, and 9) were further evaluated using density functional theory.
4 citations
TL;DR: In this paper, a single conducting polymer can be tuned to either discriminate water-, ethanol-or acetone-vapors, on demand, by changing the nature of its dopant.
4 citations
TL;DR: In this article, a solution of Bi(NO3)3 was dropped slowly into a solution containing 5-bromo-1hydroxy-2(1H)-pyridinethione (5-Br-HPT, 618 mg, 3 mmol) in EtOH (25 mL), which was then cooled to room temperature to give yellow polycrystals, which were collected by filtration, washed successively with H2O and EtOH, and dried in vacuo.
Abstract: C33H25Bi2Br6N7O7S6, P1 (no. 2), a = 13.484(1) Å, b = 13.631(1) Å, c = 15.249(1) Å, + = 94.434(1)°, * = 114.215(2)°, ( = 107.841(2)°, V = 2365.9 Å, Z = 2, Rgt(F) = 0.066, wRref(F) = 0.194, T = 298 K. Source of material A solution of Bi(NO3)3.·.5H2O (475 mg, 1 mmol) in water (15 mL) was dropped slowly into a solution of 5-bromo-1hydroxy-2(1H)-pyridinethione (5-Br-HPT, 618 mg, 3 mmol) in EtOH (25 mL). The mixed solution was stirred for 3 h at 40 °C and was then cooled to room temperature to give yellow polycrystals, which were collected by filtration, washed successively with H2O and EtOH, and dried in vacuo. Yellow square-shaped crystals suitable for X-ray analysis were obtained by recrystallization of the precipitate from N,N-dimethylformamid (m.p. 247 249 °C). Discussion Bismuth compounds have been used to treat a variety of medical disorders for over 200 years [1]. Current interest in bismuth thiolates derives in part from their ability as fungicides, antitumor agents, nanoparticle synthesis and mechanism research of bioactivity [2-5]. Although Bi(III) compounds of the Bi(mpo)3 and Bi(ph)(mpo)2 (Hmpo = 2-mercaptopyridine-N-oxide) have been prepared previously [6,7], X-ray structural data are available only for not-substituted base on the pyridine ring. The crystal structure of the title compound is a dimer with heptacoordination for each bismuth imposed by three sulfur and four oxygen atoms. Except for bridging oxygen atom O2, the coordination polyhedron around Bi1 can be described as a distorted trigonal prism with O1, S1, S4 and O3, O4, S3 at the triangular bases (dihedral angle between their mean planes 29.3(4)°, which is larger than 9.5(2)° in Bi(mpo)3) [7], different from Fe(mpo)3 [8]. In Fe(mpo)3, the arrangement of the ligands gives the complex with meridional octahedral geometry. Because of the short distances (av. 2.939 Å) of the ligands, the coordination of the bismuth atoms is distorted from regular trigonal prism with angles within chelate rings of average 68°. The present complex exhibits Bi—S bond lengths within the range from 2.646 to 2.749 Å with a mean value of 2.685 Å, shorter than in Bi(mpo)3 (2.808 Å), and Bi—O distances within the range from 2.395 to 2.783 Å with a mean value of 2.622 Å, longer than in Bi(mpo)3 (2.480 Å), but close to those in [Bi(mpo)2Ph] [6], in which the Bi—S and Bi—O bond distances are 2.674 and 2.525 Å, respectively. The relatively short C—S distances (av. 1.720 Å) as observed in [Bi(mpo)2Ph] (1.700 Å) and Bi(mpo)3 (1.707 Å) reveals partial double bond character, and nearly 0.1 Å shorter than the distance (1.81 Å) for a single bond [9]. The distances (O···S) of average 2.939 Å are similar to that in Bi(mpo)3 (2.934 Å). The three O–Bi–S angles are nearly equivalent and close to 68.00°, similar [Bi(mpo)3] (70.0°). In the surrounding of Bi1 atom, there are three five-membered ring planes Bi1/O1/N1/C1/S1 (I), Bi1/O3/ N3/C11/S3 (II) and Bi1/O4/N4/C16/S4 (III) with RMS deviation of fitted atoms of 0.276, 0.107 and 0.080 Å, respectively. The dihedral angles between planes I/II, II/III, and I/III are 69.57°, 88.80° and 31.67°, respectively. The Bi–S–C angles of average 102.2° and Bi–O–N angles of average 118.2° show that the bonding orbitals of the sulfur atoms are mainly of sp, and that of oxygen atom are of sp character, similar to H2mp complexes [10]. In the molecular packing N6, O2, O4, O6, O7, S2 and S6 form hydrogen bonds with d(C15–H···N6 ) = 3.31 Å, d(C5–H · · ·O2 ) = 3.35 Å , d(C25–H · · ·O4 ) = 3.02 Å , d(C15–H···O6 ) = 3.18 Å, d(C32–H···O7 i ) = 2.54 Å, d(C7–H···S2) = 3.63 Å, and d(C12–H···S6) = 3.65 Å, respectively, giving rise to a chain along [010] (symmetry code i: 1–x,1–y,1–z; ii: x,y,z; iii: x,1–y, 1–z; iv: x,y–1,z). The distance Bi1···Bi2 is 4.556 Å, being shorter than that in [Bi(mpo)2Ph] (4.89 Å) and longer than that in [Bi(mpo)3] (3.803 Å). Z. Kristallogr. NCS 225 (2010) 277-279 / DOI 10.1524/ncrs.2010.0120 277 © by Oldenbourg Wissenschaftsverlag, München
4 citations
TL;DR: In this article, the orthorhombic Pca21 (no. 29), a = 8.1121, b = 10.8634, c = 20.7900, V = 1832.1 Å3, Z = 4, Rgt(F) = 0.0278, wRref(F2)= 0.0574, T = 100 K.
Abstract: Abstract C10H22BiClN2O3S4, orthorhombic, Pca21 (no. 29), a = 8.1121(4) Å, b = 10.8634(5) Å, c = 20.7900(9) Å, V = 1832.1 Å3, Z = 4, Rgt(F) = 0.0278, wRref(F2) = 0.0574, T = 100 K.
3 citations
References
More filters
TL;DR: The analysis of more than five million interatomic "non-bonded" distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested.
Abstract: The distribution of distances from atoms of a particular element E to a probe atom X (oxygen in most cases), both bonded and intermolecular non-bonded contacts, has been analyzed. In general, the distribution is characterized by a maximum at short E⋯X distances corresponding to chemical bonds, followed by a range of unpopulated distances – the van der Waals gap – and a second maximum at longer distances – the van der Waals peak – superimposed on a random distribution function that roughly follows a d3 dependence. The analysis of more than five million interatomic “non-bonded” distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested for a set of more than three million data, all of them compared to over one million bond distances.
1,030 citations
TL;DR: This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc.
Abstract: Polyoxometalates (POMs) are a subset of metal oxides with unique physical and chemical properties, which can be reliably modified through various techniques and methods to develop sophisticated materials and devices. In parallel with the large number of new crystal structures reported in the literature, the application of these POMs towards multifunctional materials has attracted considerable attention. This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc. (171 references).
733 citations
TL;DR: While the overall schemes for arsenic resistance are similar in prokaryotes and eukaryotes, some of the specific proteins are the products of separate evolutionary pathways.
726 citations
TL;DR: Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour.
691 citations
TL;DR: This Account discusses another class of stable cyclic carbenes, namely, cyclic (alkyl)(amino)carbenes (CAACs), and shows that the peculiar electronic and steric properties of CAACs allow for the stabilization of unusual diamagnetic and paramagnetic main group element species.
Abstract: ConspectusCarbenes are compounds that feature a divalent carbon atom with only six electrons in its valence shell. In the singlet state, they possess a lone pair of electrons and a vacant orbital and therefore exhibit Lewis acidic and Lewis basic properties, which explains their very high reactivity. Following the preparation by our group in 1988 of the first representative, a variety of stable carbenes are now available, the most popular being the cyclic diaminocarbenes.In this Account, we discuss another class of stable cyclic carbenes, namely, cyclic (alkyl)(amino)carbenes (CAACs), in which one of the electronegative and π-donor amino substituents of diaminocarbenes is replaced by a σ-donating but not π-donating alkyl group. As a consequence, CAACs are more nucleophilic (σ-donating) but also more electrophilic (π-accepting) than diaminocarbenes. Additionally, the presence of a quaternary carbon in the position α to the carbene center provides steric environments that differentiate CAACs dramatically fr...
665 citations