Organometallic Lewis Acids LX. Pentacarbonylrhenium Complexes [(OC)5Re-L]+BF4-with N-Donor-Ligands L = Tetrazole, Dimetylaminopyridine (DMAP), Triphenyliminophosphoranes and with Triphenylphosphine Oxide

Oxygen coordination to the Xe(VI) atom of XeO3 was observed in its adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, the solid [(C6H5)3PO]2XeO3, [(CH3)2SO]3(XeO3)2, and (C5H5NO)3(XeO3)2 adducts are insensitive to mechanical shock, but undergo rapid deflagration when ignited by a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are air-stable whereas [(CH3)2SO]3(XeO3)2 slowly decomposes over several days and [(CH3)2CO]3XeO3 undergoes adduct dissociation at room temperature. The xenon coordination sphere of [(C6H5)3PO]2XeO3 is a distorted square pyramid which provides the first example of a five-coordinate XeO3 adduct. The xenon coordination spheres of the remaining adducts are distorted octahedra comprised of three Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO3. Quantum-chemical calculations were used to assess the Xe---O adduct bonds, which are predominantly electrostatic σ-hole bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the xenon atoms.

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Triphenylphosphine oxide adducts of diphenylantimony(V) and diorganotin(IV) Lewis acids: structures of SnPh2Cl2·OPPh3, SnPh2Cl2·2OPPh3, SnPh2Br2·OPPh3 and SbPh2Cl3·OPPh3

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(00)00383-1 ◽

2000 ◽

Vol 612 (1-2) ◽

pp. 53-60 ◽

Cited By ~ 24

Author(s):

D Cunningham

Keyword(s):

Lewis Acids ◽

Triphenylphosphine Oxide

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Raman and far-infrared spectra of triphenyltin isochalcocyanates and their adducts with O- and N-donor ligands: the crystal and molecular structure of isocyanato-triphenyl (pyridine-N-oxide) tin

Canadian Journal of Chemistry ◽

10.1139/v87-110 ◽

1987 ◽

Vol 65 (3) ◽

pp. 639-647 ◽

Cited By ~ 10

Author(s):

Ivor Wharf ◽

Lars Piehler ◽

Bruce M. Sailofsky ◽

Mario Onyszchuk ◽

Michel G. Simard

Keyword(s):

Direct Method ◽

Far Infrared ◽

Triphenylphosphine Oxide ◽

Donor Ligands ◽

X Ray ◽

Trigonal Bipyramidal ◽

Phenyl Rings ◽

Distorted Trigonal Bipyramidal Coordination ◽

Far Infrared Spectra ◽

Distorted Trigonal Bipyramidal

Solid state infrared and Raman data (350–100 cm−1) are reported for Ph3SnNCY (Y = O, S, Se) and their 1:1 adducts with hexamethylphosphoramide (HMPA), pyridine-N-oxide (pyO), 4-picoline-N-oxide (4-picO), triphenylphosphine oxide (Ph3PO), and pyridine (py), as well as for Ph3SnNCSe•L where L = β-pic (β-picoline) or γ-pic (γ-picoline), and assignments are given. The crystal structure of Ph3SnNCO•pyO was determined by single crystal X-ray analysis. The compound crystallizes in space group Pbca with a = 14.443(3), b = 16.676(4), c = 17.523(6) Å (−110 °C); Z = 8. The structure was solved by the direct method and refined by full-matrix least-squares methods to R = 0.024 for 2086 observed reflections. The tin atom has distorted trigonal bipyramidal coordination with the isocyanate group and pyridine-N-oxide at the apices of the bipyramid and phenyl rings in the equatorial positions. Changes in v(Sn—NCY) on adduct formation are correlated with either increased coordination at tin (Y = O) or breaking of strong chalcocyanate bridges with tin remaining five-coordinate (Y = S, Se).

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Zwitterionic Forms of Salicylaldimine Donor Ligands in Unusual Adduct Formation with Organotin(IV) Lewis Acids

Organometallics ◽

10.1021/om030540f ◽

2004 ◽

Vol 23 (5) ◽

pp. 984-994 ◽

Cited By ~ 15

Author(s):

Des Cunningham ◽

Karon Gilligan ◽

Martina Hannon ◽

Cathal Kelly ◽

Pat McArdle ◽

...

Keyword(s):

Lewis Acids ◽

Adduct Formation ◽

Donor Ligands

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Noble-Gas Chemistry More than Half a Century after the First Report of the Noble-Gas Compound

Molecules ◽

10.3390/molecules25133014 ◽

2020 ◽

Vol 25 (13) ◽

pp. 3014

Author(s):

Zoran Mazej

Keyword(s):

Lewis Acids ◽

Noble Gas ◽

Triphenylphosphine Oxide ◽

Fluoride Ion ◽

Interstellar Space ◽

Metal Centers ◽

Gas Chemistry ◽

Extreme Sensitivity ◽

Solid Argon

Recent development in the synthesis and characterization of noble-gas compounds is reviewed, i.e., noble-gas chemistry reported in the last five years with emphasis on the publications issued after 2017. XeF2 is commercially available and has a wider practical application both in the laboratory use and in the industry. As a ligand it can coordinate to metal centers resulting in [M(XeF2)x]n+ salts. With strong Lewis acids, XeF2 acts as a fluoride ion donor forming [XeF]+ or [Xe2F3]+ salts. Latest examples are [Xe2F3][RuF6]·XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6]. Adducts NgF2·CrOF4 and NgF2·2CrOF4 (Ng = Xe, Kr) were synthesized and structurally characterized at low temperatures. The geometry of XeF6 was studied in solid argon and neon matrices. Xenon hexafluoride is a well-known fluoride ion donor forming various [XeF5]+ and [Xe2F11]+ salts. A large number of crystal structures of previously known or new [XeF5]+ and [Xe2F11]+ salts were reported, i.e., [Xe2F11][SbF6], [XeF5][SbF6], [XeF5][Sb2F11], [XeF5][BF4], [XeF5][TiF5], [XeF5]5[Ti10F45], [XeF5][Ti3F13], [XeF5]2[MnF6], [XeF5][MnF5], [XeF5]4[Mn8F36], [Xe2F11]2[SnF6], [Xe2F11]2[PbF6], [XeF5]4[Sn5F24], [XeF5][Xe2F11][CrVOF5]·2CrVIOF4, [XeF5]2[CrIVF6]·2CrVIOF4, [Xe2F11]2[CrIVF6], [XeF5]2[CrV2O2F8], [XeF5]2[CrV2O2F8]·2HF, [XeF5]2[CrV2O2F8]·2XeOF4, A[XeF5][SbF6]2 (A = Rb, Cs), Cs[XeF5][BixSb1-xF6]2 (x = ~0.37–0.39), NO2XeF5(SbF6)2, XeF5M(SbF6)3 (M = Ni, Mg, Zn, Co, Cu, Mn and Pd) and (XeF5)3[Hg(HF)]2(SbF6)7. Despite its extreme sensitivity, many new XeO3 adducts were synthesized, i.e., the 15-crown adduct of XeO3, adducts of XeO3 with triphenylphosphine oxide, dimethylsulfoxide and pyridine-N-oxide, and adducts between XeO3 and N-bases (pyridine and 4-dimethylaminopyridine). [Hg(KrF2)8][AsF6]2·2HF is a new example of a compound in which KrF2 serves as a ligand. Numerous new charged species of noble gases were reported (ArCH2+, ArOH+, [ArB3O4]+, [ArB3O5]+, [ArB4O6]+, [ArB5O7]+, [B12(CN)11Ne]−). Molecular ion HeH+ was finally detected in interstellar space. The discoveries of Na2He and ArNi at high pressure were reported. Bonding motifs in noble-gas compounds are briefly commented on in the last paragraph of this review.

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Adducts of triphenyllead isothiocyanate and selenocyanate with some O- and N-donor ligands

Canadian Journal of Chemistry ◽

10.1139/v83-138 ◽

1983 ◽

Vol 61 (4) ◽

pp. 743-749 ◽

Cited By ~ 2

Author(s):

Ryszard Wojtowski ◽

Ivor Wharf ◽

Mario Onyszchuk

Keyword(s):

Solid State ◽

Infrared Spectra ◽

Benzene Solution ◽

Triphenylphosphine Oxide ◽

Donor Ligands ◽

Amine Adducts ◽

Bonding Mode ◽

Infrared Data

The preparation and properties of triphenyllead selenocyanate have been reinvestigated. Infrared spectra show that the solid is polymeric with strong Pb—Se and weak Pb—N bonds; in benzene or CH2Cl2 solutions ν(CN) values are consistent with the Ph3PbSeCN bonding mode. The first 1:1 adducts of triphenyllead selenocyanate with hexamethylphosphoramide (HMPA), pyridine-N-oxide (pyO), 4-picoline-N-oxide (4-picO), and triphenylphosphine oxide (TPPO) have been prepared; infrared data show that Ph3PbSeCN•L (L = pyO, 4-picO, TPPO) are selenocyanates, but the HMPA adduct is an isoselenocyanate. The adducts dissociate in benzene and ν(CN) frequencies show that both N-bonded and Se-bonded adduct isomers are present. In contrast, the adducts Ph3PbNCS•L (L = HMPA, pyO, 4-picO, TPPO) are N-bonded in the solid state and in benzene solution where they are undissociated. Amine adducts, Ph3PbNCS•L (L = pyridine, β-picoline, γ-picoline, pyrrolidine (pyrrol), piperidine (pipy), cyclohexylamine (CyNH2)) and Ph3PbNCS•2L (L = morpholine (morph)), as well as Ph3PbNCSe•pipy and 2 Ph3PbNCSe•3L (L = pyrrol or morph) have been prepared, but these are less stable than adducts with O-donor ligands. Infrared data suggest that amine adducts of Ph3PbNCS have N-bonded and/or ionic thiocyanate groups while all Ph3PbSeCN–amine adducts contain the selenocyanate ion.

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Spectroscopic studies of triphenyltin azide and of its adducts with O- and N-donor ligands; the crystal and molecular structures of triphenyltin azide and of azido(hexamethylphosphoramide)triphenyltin(IV)

Canadian Journal of Chemistry ◽

10.1139/v98-207 ◽

1998 ◽

Vol 76 (12) ◽

pp. 1827-1835 ◽

Cited By ~ 11

Author(s):

Ivor Wharf ◽

Ryszard Wojtowski ◽

Carol Bowes ◽

Anne-Marie Lebuis ◽

Mario Onyszchuk

Keyword(s):

Solid State ◽

Spectroscopic Studies ◽

Triphenylphosphine Oxide ◽

Molecular Structures ◽

The Other ◽

Donor Ligands ◽

X Ray ◽

Crystal And Molecular Structures ◽

Nmr Data ◽

Ir And Raman

Complete far-IR and Raman data (<400 cm-1) are reported for triphenyltin azide (1) as well as for adducts Ph3SnN3·L (L = hexamethylphosphoramide (HMPA), triphenylphosphine oxide, pyridine-N-oxide, 4-picoline-N-oxide, or pyridine). The small changes in v(Sn-N3) noted on going from (1) to the adducts, as well as solid-state 119Sn nmr data, indicate that (1), like the adducts, has five-coordinate tin atoms. X-ray analysis shows that (1) crystallizes with two different chains of five-coordinate Ph3Sn units joined by 1,3-azide bridges. In one unit, the geometry around tin is similar to that found for the monomeric HMPA adduct (2), which has trans-axial HMPA and azide ligands. The other unit in (1) has nonplanar -SnC3- groups connected by less symmetric 1,3-azide bridges and thus resembles the structure of isoelectronic triphenyltin isocyanate.Key words: triphenyltin azide, O- and N-donor adducts, far-IR/Raman, crystal structures.

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Synthesis and vibrational spectra of tin(II) isothiocyanate adducts with some O- and N-donor ligands

Canadian Journal of Chemistry ◽

10.1139/v78-333 ◽

1978 ◽

Vol 56 (15) ◽

pp. 2039-2041 ◽

Cited By ~ 6

Author(s):

Tewfik B. Absi ◽

Ramesh C. Makhija ◽

Mario Onyszchuk

Keyword(s):

Molecular Weight ◽

Powder Diffraction ◽

Triphenylphosphine Oxide ◽

Donor Ligands ◽

Infrared And Raman Spectra ◽

Powder Diffraction Data ◽

Nitrogen Donor Ligands ◽

X Ray ◽

Oxygen Donor ◽

Nitrogen Donor

Five new adducts of Sn(NCS)2 have been prepared and characterized: Sn(NCS)2•2L (L = 2,6-dimethyl-y-pyrone and N,N-dimethylacetamide), Sn(NCS)2•LL (LL = 1,10-phenanthroline and 2,2′-bipyridine), and Sn(NCS)(ox) (ox = 8-hydroxyquinolinate). By comparing their infrared and Raman spectra with those of SnX2•L (X = Cl, NCS; L = triphenylphosphine oxide), SnX2•2L (X = Cl, NCS; L = dimethylsulphoxide and pyridine-N-oxide), SnCl2•LL (LL = 1,10-phenanthroline and 2,2′-bipyridine), and SnCl(ox), assignments have been made for v(CN), v(CS), and δ(NCS) vibrations; these suggest the presence of N-bonded and —NCS— bridge-bonded thiocyanate groups. Molecular weight, conductivity, and X-ray powder diffraction data support the conclusion that the adducts with the oxygen donor ligands are molecular with only N-bonded thiocyanate groups. Adducts with the bidentate nitrogen donor ligands are polymeric and have —NCS— bridging and N-bonded thiocyanate.

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Xenon Trioxide Adducts of O-Donor Ligands; [(CH3)2CO]3XeO3, [(CH3)2SO]3(XeO3)2, (C5H5NO)3(XeO3)2, and [(C6H5)3PO]2XeO3

10.26434/chemrxiv.7092263 ◽

2018 ◽

Author(s):

Katherine Marczenko ◽

James Goettel ◽

Gary Schrobilgen

Keyword(s):

Room Temperature ◽

Triphenylphosphine Oxide ◽

Donor Ligands ◽

Mechanical Shock ◽

X Ray Diffraction ◽

X Ray ◽

Oxygen Coordination ◽

Xenon Trioxide ◽

Distorted Octahedra ◽

Coordination Spheres

Oxygen coordination to the Xe(VI) atom of XeO3 was observed in its adducts with triphenylphosphine oxide, dimethylsulfoxide, pyridine-N-oxide, and acetone. The crystalline adducts were characterized by low-temperature, single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, the solid [(C6H5)3PO]2XeO3, [(CH3)2SO]3(XeO3)2, and (C5H5NO)3(XeO3)2 adducts are insensitive to mechanical shock, but undergo rapid deflagration when ignited by a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are air-stable whereas [(CH3)2SO]3(XeO3)2 slowly decomposes over several days and [(CH3)2CO]3XeO3 undergoes adduct dissociation at room temperature. The xenon coordination sphere of [(C6H5)3PO]2XeO3 is a distorted square pyramid which provides the first example of a five-coordinate XeO3 adduct. The xenon coordination spheres of the remaining adducts are distorted octahedra comprised of three Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO3. Quantum-chemical calculations were used to assess the Xe---O adduct bonds, which are predominantly electrostatic σ-hole bonds between the nucleophilic oxygen atoms of the bases and the σ-holes of the xenon atoms.

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Adducts of diphenyllead diselenocyanate with some O- and N-donor ligands

Canadian Journal of Chemistry ◽

10.1139/v85-560 ◽

1985 ◽

Vol 63 (12) ◽

pp. 3398-3402

Author(s):

Ivor Wharf ◽

Ryszard Wojtowski ◽

Mario Onyszchuk

Keyword(s):

Infrared Spectra ◽

Triphenylphosphine Oxide ◽

Dimethyl Sulphoxide ◽

Donor Ligands ◽

Complete Ionization ◽

Amine Adducts ◽

Infrared Data

The preparation and properties of Ph2Pb(SeCN)2 have been reinvestigated. Infrared spectra show that the solid is polymeric with stronger Pb—Se and weaker Pb—N bonds. In N,N-dimethylformamide (DMF) solution v(CN) values are consistent with complete ionization to NCSe−, but coordinated N- and Se-bound selenocyanate species are observed when DMF/CH2CI2 mixtures are used as solvents. The first 1:2 adducts of Ph2Pb(SeCN)2 with hexamethylphosphoramide (HMPA), triphenylphosphine oxide (Ph3PO), pyridine-N-oxide (pyO), 2,4,6-collidine-N-oxide (collO), and dimethyl sulphoxide (DMSO) have been prepared, while with 4-picoline-N-oxide (4-picO) a 1:4 adduct is obtained. Infrared data show Ph2Pb(SeCN)2•2L (L = HMPA, Ph3PO, collO) are in fact isoselenocyanates, but the pyO and DMSO adducts are selenocyanates. Amine adducts Ph2Pb(SeCN)2•2L (L = morpholine (morph), quinoline (quin), piperidine (pipy)) and Ph2Pb(SeCN)2•3LL (LL = α.α′-dipyridyl (dipy), 1,10-phenanthroline (phen)) have been prepared. Infrared data suggest that amine adducts most probably have N-bonded selenocyanate groups, in some cases with ionic selenocyanate also present. The adduct with 4-picO also contains ionic selenocyanate.

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