2629-47-2Relevant articles and documents
Electrochemical synthesis of organoantimony compounds and their coordination compounds
Rala, Sarbjit
, p. 642 - 646 (2019)
Electrochemical reactions of bromoethane, 1-bromopropane, 1-chlorobutane and chlorobenzene have been carried out in acetonitrile at sacrificial antimony anode using tetrabutylammonium chloride as supporting electrolyte. The products isolated from the anod
Compounds of the types Pn(pyS)3(Pn = P, As, Bi; PyS: Pyridine-2-thiolate) and Sb(pyS)xPh3-x(x = 3-1); Molecular structures and electronic situations of the Pn atoms
W?chtler, Erik,Gericke, Robert,Block, Theresa,Gerke, Birgit,P?ttgen, Rainer,Wagler, J?rg
, p. 103 - 118 (2021)
The compounds Pn(pyS)3 (Pn = P, As, Sb, Bi) were synthesized from the respective chloride (Pn = P, As, Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethylamine (NEt3) as a supporting base in THF (P, Sb), CHCl3 (As) or methanol (Bi). Sb(pyS)3 was also obtained from the reaction of SbCl3 with LipyS (prepared in situ) in methanol. The compounds Sb(pyS)2Ph and Sb(pyS)Ph2 were prepared in a one-pot reaction starting from SbCl3 and SbPh3 (1:1 ratio). Upon Cl/pyS substitution, the resulting reaction mixture allows for a facile separation of the products in hot hexane. P(pyS)3 and As(pyS)3 crystallize isostructurally to the reported structure of Sb(pyS)3 with κ-S-bound pyS ligands. These crystal structures feature close Pn···Pn contacts which are most pronounced for the arsenic derivative. Bi(pyS)3 adopts a different molecular structure in the solid state, which features two chelating (κ2-S,N-pyS) ligands and a κ-S-bound ligand. The presence of N→Bi interactions between the nitrogen atom of the κ-S-pyS ligand and the Bi atom of another molecule renders this structure a polymer chain along the crystallographic b axis with BiBi van-der-Waals contacts. The structures of this set of Pn(pyS)3 compounds were also studied in solution using 1H NMR spectroscopy, revealing equivalent pyS ligands in discrete Pn(pyS)3 molecules. The molecular structure of Sb(pyS)Ph2 was optimized by quantum chemical methods, and a comparison with the structures reported for the other Sb/pyS/Ph combinations reveals Sb(pyS)2Ph to feature the strongest Sb···N interactions with the κ-S-pyS ligand. The results of 1H NMR spectroscopic investigations of the compounds Sb(pyS)xPh3-x (x = 3-0) suggest the Ph protons in ortho position to be incorporated into intramolecular C-H···S contacts for x = 2 and 1. Natural localized molecular orbital (NLMO) calculations were employed in order to gain insights into the electronic situations of the Pn atoms and Pn-R bonds (R = S, C), especially for the effects caused by formal substitution of Pn in the compounds Pn(pyS)3 and the ligand patterns in the compounds Sb(pyS)xPh3-x (x = 3-0). For the latter series of compounds, the electronic situation of the Sb atom was further studied by 121Sb M?ssbauer spectroscopy, providing a correlation between the calculated electron density at Sb [ρ(0)] and the experimentally observed isomer shift δ. The missing link between group 15 and group 13 metal compounds of the type M(pyS)3, compound Al(pyS)3, was synthesized in this work. In the solid state (confirmed crystallographically), the mer isomer of this tris-chelate complex with distorted octahedral Al coordination sphere was found. This coordination mode was confirmed for the solution state (CDCl3) by 1H and 13C NMR spectroscopy at T = -40 °C.
Catalysis with Pnictogen, Chalcogen, and Halogen Bonds
Benz, Sebastian,Poblador-Bahamonde, Amalia I.,Low-Ders, Nicolas,Matile, Stefan
supporting information, p. 5408 - 5412 (2018/03/23)
Halogen- and chalcogen-based σ-hole interactions have recently received increased interest in non-covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and mon
Syntheses, Structures, and Characterization of Nickel(II) Stibines: Steric and Electronic Rationale for Metal Deposition
Taylor, William V.,Xie, Zhu-Lin,Cool, Nicholas I.,Shubert, Sofia A.,Rose, Michael J.
, p. 10364 - 10374 (2018/08/28)
Reactions of the homoleptic and heteroleptic antimony ligands SbiPr3, SbiPr2Ph, SbMe2Ph, and SbMePh2 with NiI2 generate rare NiII stibine complexes in either square planar or trigonal bipyramidal (TBP) geometries, depending on the steric size of the ligands. Tolman electronic parameters were calculated (DFT) for each antimony ligand to provide a tabulated resource for the relative strengths of simple antimony ligands. The electronic absorbance spectra of the square planar complexes exhibit characteristic bands [λmax ≈ 560 nm (17 900 cm-1), ? ≈ 4330 M-1 cm-1] at lower energies compared to the reported phosphine complexes, indicating the weak donor strength of the stibine ligands and resultant low-energy ligand field d→d transitions. The square planar complex Ni(I)2(SbiPr3)2 reacts with CO to form the TBP complex Ni(I)2(SbiPr3)2(CO). Lastly, the complexes were investigated for nickel metal deposition on Si|Cu(100 nm) substrates. The complexes with the strongest donating ligand, SbiPr3, deposited the purest layer of NiCu alloy according to the balanced reaction Ni(I)2(SbIIIiPr3)2 → Ni0 + SbV(iPr3)I2; the iodinated SbV byproduct was unambiguously detected in the supernatant by 1H NMR and mass spectrometry. Complexes with weaker ligands (poor I2 acceptors/scavengers) resulted undesired deposition of iodine and CuI on the surface. This work thus serves as a guide for the design and synthesis of 3d metal complexes with neutral, heavy main-group donors that are useful for metal deposition applications.
Synthesis and characterization of rhodium, iridium, and palladium complexes of a diarylamido-based PNSb pincer ligand
Kosanovich, Alex J.,Jordan, Aldo M.,Bhuvanesh, Nattamai,Ozerov, Oleg. V.
, p. 11619 - 11624 (2018/08/28)
A new diarylmido-based pincer proto ligand (iPrPNHSbPh) with one -PPri2 and one -SbPh2 side donor has been synthesized. Three complexes of its amido form were prepared using standard metalation techniques: (iPrPNSbPh)PdCl, (iPrPNSbPh)RhCO, and (iPrPNSbPh)Ir(COE), where COE = cis-cyclooctene. These complexes were compared with their previously reported analogs incorporating a -PPh2 side donor in place of -SbPh2. The -SbPh2 donor arm is less donating towards the metal and is less strongly trans-influencing, based on the structural and IR spectroscopic analysis of the Rh complexes. The redox potential of the Pd complexes is only marginally affected by the change from -PPh2 to -SbPh2. (iPrPNSbPh)Ir(COE) proved to be a slower and less selective catalyst in the dehydrogenative borylation of terminal alkynes (DHBTA) than its -PPh2 analog.
Coordination of a stibine oxide to a Lewis acidic stiborane at the upper rim of the biphenylene backbone
Chen, Chang-Hong,Gabba?, Fran?ois P.
supporting information, p. 12075 - 12078 (2018/09/25)
Our interest in bifunctional antimony Lewis acids has led us to synthesize 1,8-bis(diphenylstibino)biphenylene (2) by reaction of 1,8-bis(trimethylstannyl)biphenylene (1) with Ph2SbCl. Oxidation of this distibine with o-chloranil, followed by work-up in air afforded a biphenylene derivative (3) featuring a triarylstibine oxide connected via an Sb═O → Sb bridge to the neighbouring antimony(v) center.
Structural, spectroscopic and computational examination of the dative interaction in constrained phosphine-stibines and phosphine-stiboranes
Chalmers, Brian A.,Bühl, Michael,Athukorala Arachchige, Kasun S.,Slawin, Alexandra M. Z.,Kilian, Petr
supporting information, p. 7520 - 7531 (2015/05/13)
Abstract A series of phosphine-stibine and phosphine-stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups -SbClnPh4-n (5-9), as well as trivalent groups -SbCl2, -Sb(R)Cl, and -SbPh2 (2-4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P-Sb dative interactions in both series range from strongly bonding to non-bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P-Sb distance is observed between -SbClPh3 and -SbCl2Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non-bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the SbIII series, two geometric forms are observed. The P-Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine-stiborane complexes 5-9 represent the first examples of the σ4P→σ6Sb structural motif. A complex situation: The strength of a dative phosphine-stiborane (P-Sb) interaction increases with stepwise replacement of phenyl groups on antimony atom with chloride groups. As the Lewis acidity is increased in regular steps (see figure), essentially linear response is observed initially, however then a sudden change in the P-Sb distance takes place during one particular step. This is consistent with a sudden switch from a non-bonding to a bonding interaction, that is, a discrete rather than continuum response.
Cage-like Carboxyl bridged octaphenyltetraantimony compounds (SbPh2)4(μ-O)4(μ-OH)2(μ- O2CR)2: Synthesis and structural characterization
Yin, Handong,Wu, Qingkun,Hong, Min,Li, Wenkuan
, p. 725 - 729 (2012/07/14)
The metal-directed self-assembly of biphenylantimony trichloride and homocarboxylic acids LH [L = 2-CHO-C6H4COO- (1), 2, 3-2F-C6H4COO- (2), 4-CF 3-C6H4COO- (3)] provided three novel tetranuclear organoantimony(V) complexes, which were characterized by elemental analysis, FT-IR, 1H, and 13C NMR spectroscopy as well as melting point, and X-ray single crystal analysis. In the molecular structure, four hexacoordinate antimony atoms are linked into a [Sb2(μ-O) 2]2(μ-O)2 cage architecture by oxo-bridges which are terminally bridged by two carboxyl groups. Copyright
Promotion of phosphaalkyne cyclooligomerisation by a Sb(V) to Sb(III) redox process
Fish, Cheryl,Green, Michael,Kilby, Richard J.,McGrady, John E.,Pantazis, Dimitrios A.,Russell, Christopher A.
, p. 3753 - 3758 (2009/02/02)
A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[4.2.0. 02,5]octa-3,7-diene, is obtained from reaction of the zirconocene 1,3-diphosphabicyclo[1.1.0]butane with Ph2SbCl3 in THF or CH2Cl2. Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph2SbCl and 1,3-diphosphabicyclo[1.1.0]butane plays a pivotal role in the reaction. The zwitterionic character of this intermediate species allows it to act simultaneously as both an ene and an eneophile, and a symmetry-allowed bimolecular reaction leads to the tetraphosphaladderene species via a spirocyclic intermediate.
Silicon-lead chalcogenides of the types Me4Si2(E)2PbPh2 and Ph2Pb(E)2Si2Me2 (E)2PbPh2 (E = S, Se) and related compounds containing tin and antimony
Herzog, Uwe,Rheinwald, Gerd
, p. 220 - 225 (2007/10/03)
The reaction of a 1:1 mixture of Ph2PbCl 2 and ClSiMe2-SiMe2Cl with H2S/NEt3 yielded the mixed silicon-lead sulfide Me4Si2(S)2PbPh2 (1a), a bicyclic silicon lead sulfide, Ph2Pb(S) 2Si2Me2(S)2PbPh2 (1b) was obtained by similar treatment of a 2:1 mixture of Ph2 PbCl2 and Cl2SiMe-SiMeCl2. The corresponding selenium compounds (2a-b) were obtained by reactions of mixtures of Ph2PbCl2 and methylchlorodisilanes with Li2Se in THF. All products were characterized by multinuclear (1H, 13C, 29Si, 77Se and 207Pb) NMR spectroscopy. The molecular structure of 1a is reported revealing a central five membered ring Si2S2Pb in envelope conformation with one sulfur atom (S1) above the plane defined by the atoms Pb1-S2-Si2-Si1. For comparison, the tin compounds Me4Si2(Se) 2SnPh2 (4a), and Ph2Sn(Se) 2Si2Me2(Se)2SnPh2 (4b) have also been prepared essentially applying the same procedure as for compounds 2a-b. A plot of δ (207Pb) of 1a-2b versus δ (119Sn) of the corresponding tin compounds 3a-4b exhibits a linear correlation with a slope of 4.11 (±0.17). Attempts to build related cycles containing a Group 15 element led to the isolation of the antimony compounds Me4Si2 (E)2SbPh (5a: E = S, 5b: E = Se) starting from ClSiMe2-SiMe2-SiMe2Cl, PhSbCl2 and either H2S/NEt3 or Li2Se.
