Experimental and calculated molecular structures and high symmetry conformations of [Sb2F11]− (D4h) and 1,4-C4H4N2·2SbF5 (D2h)

Sham, Iona H. T.; Patrick, Brian O.; Ahsen, Britta von; Ahsen, Stefan von; Willner, Helge; Thompson, Robert C.; Aubke, F.

doi:10.1016/s1293-2558(02)00036-5

Cited by 24 publications

(29 citation statements)

References 40 publications

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“…111 complexes, geometries observed in crystals adhere to the square pyramidal shapes illustrated in Fig. 1 for pentavalent PF5, [77][78][79][80] AsF5, [81][82][83][84][85][86][87][88][89][90] and SbF5 [91][92][93] adducts with miscellaneous N-donors including heteroaromatics, azoles, pyridine derivatives and linear aliphatic molecules.…”

Section: Discussionmentioning

confidence: 66%

“…Nor is this an uncommon bonding situation for pnicogen atoms so its examination will be of some real relevance. [77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92][93] ZF5, was thus taken as pnicogen-bonding molecule, with Z=P, As, and Sb, to again determine dependence upon size of pnicogen atoms. Three different bases were considered so as to cover a range of electron-donating power.…”

Section: Systems and Methodsmentioning

confidence: 99%

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Implications of monomer deformation for tetrel and pnicogen bonds

Zierkiewicz

Michalczyk

Scheiner

2018

Phys. Chem. Chem. Phys.

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A series of TF4 and ZF5 molecules (T = Si, Ge, Sn and Z = P, As, Sb) were allowed to engage in tetrel and pnicogen bonds, respectively, with NH3, pyrazine, and HCN. The interaction energies are quite large, approaching 50 kcal mol-1 in some cases. The formation of each complex is accompanied by substantial geometrical deformation of the Lewis acid to accommodate the approaching base. The energy associated with this monomer rearrangement is the largest for the smaller central atoms Si and P, where it exceeds 20 kcal mol-1. The total reaction energy of binding, which takes this distortion energy into account, is thus significantly lower than the interaction energy, although remaining quite high, particularly for the larger Sn and Sb central atoms. The tetrel and pnicogen bonds can still form even if the Lewis acid is not permitted to adjust its internal geometry, but they are drastically weakened, dropping by as much as 95%. The monomer rearrangement also aids in the binding by intensifying its σ-hole by a factor of 1.5-2.9.

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Section: Discussionmentioning

confidence: 66%

Section: Systems and Methodsmentioning

confidence: 99%

Implications of monomer deformation for tetrel and pnicogen bonds

Zierkiewicz

Michalczyk

Scheiner

2018

Phys. Chem. Chem. Phys.

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“…(ii) As discussed previously, , in [Sb 2 F 11 ] - salts with superelectrophilic 5 σ-carbonyl cations, ,,,,,,,, the [Sb 2 F 11 ] - is distorted from its equilibrium D 4 h conformation 83 by bending and rotational processes toward C 1 symmetry, which are measured in terms of the bridge angle α and the dihedral angle ψ . In salts with unipositive cations such as [Au(CO) 2 ] + 17,83 and [Rh(CO) 4 ] + , , the D 4 h conformation of [Sb 2 F 11 ] - is retained. Also in [Re(CO) 6 ][Re 2 F 11 ], the related [Re 2 F 11 ] - anion has D 4 h symmetry.…”

Section: Discussionmentioning

confidence: 88%

“…(i) While the molecular geometries for octahedral, trigonal-bipyramidal, square-planar, and linear metal carbonyl cations are very regular (see Figures −6) as discussed before, only the M−C−O bond angles will invariably depart from linearity by about 2−4° . This is explained by secondary interactions 82 of C atoms of the cations with F atoms of the anions. , (ii) The [Sb 2 F 11 ] - anions are extensively distorted from the D 4 h ground-state conformation, by bending and rotation of the equatorial SbF 4 groups in the dioctahedral anion. The distortions are expressed in terms of the Sb−F−Sb bridge angle α and the dihedral angle ψ. , In [Sb 2 F 11 ] - salts with unipositive cations such as [Au(CO) 2 ] + 17 and [Rh(CO) 4 ] + , with the latter studied only by vibrational spectroscopy, the anion is undistorted and has D 4 h symmetry.…”

Section: Discussionmentioning

confidence: 99%

σ-Bonded Metal Carbonyl Cations and Their Derivatives: Syntheses and Structural, Spectroscopic, and Bonding Principles

Willner

Aubke

2003

Organometallics

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Homoleptic σ-bonded metal carbonyl cations (σ-carbonyls) and their derivatives have grown in recent years into a large subgroup of mononuclear metal carbonyl complexes. They are at present formed by 17 elements, including the post transition metal mercury. Most are generated in superacids: the Lewis superacid SbF 5 and the conjugate Brønsted-Lewis superacid HF-SbF 5 . Thermally stable salts are formed with the superacid anions [Sb 2 F 11 ] -and [SbF 6 ] -. Many of the cations are superelectrophilic, with metals in oxidation states of +2 or +3. Three different synthetic routes are developed: reductive (A) or solvolytic carbonylations (B) and oxidative methods (C). Considerable progress has been made by replacing the Lewis superacid SbF 5 as reaction medium by the conjugate Brønsted-Lewis superacid HF-SbF 5 . This allows reactions to proceed faster in a homogeneous phase and to produce crystalline materials. In total 27 mostly recent molecular structures have been obtained, including that of [Ir(CO) 6 ][SbF 6 ] 3 ‚4HF, the first HF solvate with one of the HF molecules coordinated in an isotridentate mode to three carbon atoms of the cation. Due to the electrophilic nature of the carbonyl carbon in fluoroantimonate salts of metal carbonyl cations, extended structures are formed via significant interionic C---F contacts. A new σ-bonded carbonyl, (CF 3 ) 3 BCO, which has been fully characterized, expands the existence range of metal carbonyl cations to group 13. The large amount of spectroscopic and structural information accumulated is used to present a conceptually simple bonding model.

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“…With almost linear dihedral angle (approx. 171°) and very small torsion angle (7°, Table 2) the [Sb 2 F 11 ] – anion (Figure 4) is very closed to ideal D 4 h symmetry 25…”

Section: Resultsmentioning

confidence: 99%

Polyethyleneimine‐Functionalized Polyamide Imide (Torlon) Hollow‐Fiber Sorbents for Post‐Combustion CO₂ Capture

Qiu

Lively³

et al. 2013

ChemSusChem

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Carbon dioxide emitted from existing coal-fired power plants is a major environmental concern due to possible links to global climate change. In this study, we expand upon previous work focused on aminosilane-functionalized polymeric hollow-fiber sorbents by introducing a new class of polyethyleneimine (PEI)-functionalized polymeric hollow-fiber sorbents for post-combustion carbon dioxide capture. Different molecular weight PEIs (M(n) ≈600, 1800, 10,000, and 60,000) were studied as functional groups on polyamide imide (PAI, Torlon) hollow fibers. This imide ring-opening modification introduces two amide functional groups and was confirmed by FTIR attenuated total reflectance spectroscopy. The carbon dioxide equilibrium sorption capacities of PEI-functionalized Torlon materials were characterized by using both pressure decay and gravimetric sorption methods. For equivalent PEI concentrations, PAI functionalized with lower molecular weight PEI exhibited higher carbon dioxide capacities. The effect of water in the ring-opening reaction was also studied. Up to a critical value, water in the reaction mixture enhanced the degree of functionalization of PEI to Torlon and resulted in higher carbon dioxide uptake within the functionalized material. Above the critical value, roughly 15% w/w water, the fiber morphology was lost and the fiber was soluble in the solvent. PEI-functionalized (Mn ≈600) PAI under optimal reaction conditions was observed to have the highest CO2 uptake: 4.9 g CO2 per 100 g of polymer (1.1 mmol g(-1)) at 0.1 bar and 35 °C with dry 10% CO2/90% N2 feed for thermogravimetric analysis. By using water-saturated feeds (10% CO2 /90% N2 dry basis), CO2 sorption was observed to increase to 6.0 g CO2 per 100 g of sorbent (1.4 mmol g(-1)). This material also demonstrated stability in cyclic adsorption-desorption operations, even under wet conditions at which some highly effective sorbents tend to lose performance. Thus, PEI-functionalized PAI fibers can be considered as promising material for post-combustion CO2 capture.

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Experimental and calculated molecular structures and high symmetry conformations of [Sb2F11]− (D4h) and 1,4-C4H4N2·2SbF5 (D2h)

Cited by 24 publications

References 40 publications

Implications of monomer deformation for tetrel and pnicogen bonds

Implications of monomer deformation for tetrel and pnicogen bonds

σ-Bonded Metal Carbonyl Cations and Their Derivatives: Syntheses and Structural, Spectroscopic, and Bonding Principles

Polyethyleneimine‐Functionalized Polyamide Imide (Torlon) Hollow‐Fiber Sorbents for Post‐Combustion CO₂ Capture

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Experimental and calculated molecular structures and high symmetry conformations of [Sb2F11]− (D4h) and 1,4-C4H4N2·2SbF5 (D2h)

Cited by 24 publications

References 40 publications

Implications of monomer deformation for tetrel and pnicogen bonds

Implications of monomer deformation for tetrel and pnicogen bonds

σ-Bonded Metal Carbonyl Cations and Their Derivatives: Syntheses and Structural, Spectroscopic, and Bonding Principles

Polyethyleneimine‐Functionalized Polyamide Imide (Torlon) Hollow‐Fiber Sorbents for Post‐Combustion CO2 Capture

Contact Info

Product

Resources

About

Polyethyleneimine‐Functionalized Polyamide Imide (Torlon) Hollow‐Fiber Sorbents for Post‐Combustion CO₂ Capture