Ten-Vertex Polyhedral Monocarbaborane Chemistry. The Novel High-Yield Formation of the Ten-Vertex closo Compound [6-(PMe2Ph)-closo-1-CB9H9] from the Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11]

1993 ◽  
Vol 58 (12) ◽  
pp. 2924-2935 ◽  
Author(s):  
Jane H. Jones ◽  
Bohumil Štíbr ◽  
John D. Kennedy ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
High Yield ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Centre ◽  
X Ray ◽  
Yield Formation ◽  
Boiling Toluene

Thermolysis of [8,8-(PMe2Ph)2-nido-8,7-PtCB9H11] in boiling toluene solution results in an elimination of the platinum centre and cluster closure to give the ten-vertex closo species [6-(PMe2Ph)-closo-1-CB9H9] in 85% yield as a colourles air stable solid. The product is characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystals (from hexane-dichloromethane) are monoclinic, space group P21/c, with a = 903.20(9), b = 1 481.86(11), c = 2 320.0(2) pm, β = 97.860(7)° and Z = 8, and the structure has been refined to R(Rw) = 0.045(0.051) for 3 281 observed reflections with Fo > 2.0σ(Fo). The clean high-yield elimination of a metal centre from a polyhedral metallaborane or metallaheteroborane species is very rare.

Eleven-Vertex Polyhedral Dicarbaplatinaborane Chemistry. Aspects of the Chemistry of Some closo-Structured {1,2,3-PtC2B8} Species and Some Related Compounds

1993 ◽  
Vol 58 (9) ◽  
pp. 2090-2120 ◽  
Author(s):  
John D. Kennedy ◽  
Bohumil Štíbr ◽  
Tomáš Jelínek ◽  
Xavier L. R. Fontaine ◽  
Mark Thornton-Pett
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
General Behaviour ◽  
Space Group ◽  
X Ray ◽  
Metal Bonding ◽  
Related Compounds

The reaction of the ten-vertex nido anions [6,9-C2B8H10]2-, [6-Me-6,9-C2B8H9]2- and [6-Ph-6,9-C2B8H9]2- with [cis-PtCl2(PMe2Ph)2] in CH2Cl2 yields the yellow crystalline closo-structured eleven-vertex compounds [2-X-1,1-(PMe2Ph)2-1,2,3-PtC2B8H9], where X = H (compound 1), Me (compound 2), or Ph (compound 3) in yields of 58 88%. These compounds have been characterized by multielement NMR spectroscopy and, in the case of compounds 1 and 2, by single-crystal X-ray diffraction analysis. Crystals of compound 1 were monoclinic, space group P21/n, with a = 947.6(1), b = 1 547.7(3), c = 1 804.0(3) pm, β = 104.78(1)°, and Z = 4, solved and refined to R (Rw) = 0.0216 (0.0234) with 4 200 unique reflections I > 2.0 σ(I). Crystals of compound 2 were monoclinic, space group I2/a (= C2/c), with a = 1 824.8(2), b = 1 016.8(2), c = 1 328.2(3) pm, β = 101.48(2)°, and Z = 4, solved and refined to R (Rw) = 0.0442 (0.0474) with 2 057 unique reflections I > 2.0 σ(I). The NMR and X-ray results reveal that the closed eleven-vertex compounds [2-X-1,1-(PR3)2-1,2,3-PtC2B8H9] exhibit a previously unsuspected but very free contrarotational fluxionality within the constrains of their η6-carborane-to-metal bonding that is accompanied by a marked flexing of the η6-{C2B8H9X} moiety between nido and arachno ten-vertex geometries and electronic characteristics. The structural and bonding implications are discussed and elucidated specifically with reference to the NMR and geometrical charcteristics of [closo-2,3- C2B9H11], [arachno-6,9- C2B8H14] and the [nido-6-X-6,9- C2B8H9]2- anions, together with other pertinent species such as [μ-6,9-(SnMe2)-nido-6,9-C2B8H10] and more generally with reference to other eleven-vertex metallaheteroborano species. The general behaviour patterns thus established are summarized.

scholarly journals Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 3920
Author(s):  
Martin Weber ◽  
Gábor Balázs ◽  
Alexander V. Virovets ◽  
Eugenia Peresypkina ◽  
Manfred Scheer
Keyword(s):  
Diffraction Analysis ◽  
Room Temperature ◽  
31P Nmr ◽  
Spectroscopic Studies ◽  
Iron Complex ◽  
The Novel ◽  
X Ray Diffraction ◽  
X Ray ◽  
Phosphenium Ions

By reacting [{Cp‴Fe(CO)2}2(µ,η1:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]− = [OTf]− = [O3SCF3]−, [PF6]−), a mixture of two main products of the composition [{Cp‴Fe(CO)2}2(µ,η1:1-P5(C6H5)2)][PF6] (2a and 3a) could be identified by extensive 31P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η4:1-P5Ph2){Cp‴(CO)2Fe}][PF6] (4) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO)2}4(µ4,η1:1:1:1-P8)][OTf]2 (5) containing a tetracyclo[3.3.0.02,7.03,6]octaphosphaoctane ligand.

Megastachine, a new alkaloid from Lycopodiummegastachyum

1979 ◽  
Vol 57 (13) ◽  
pp. 1691-1693 ◽  
Author(s):  
Jean-Claude Braekman ◽  
Claude Hootele ◽  
Noah Miller ◽  
Jean-Paul Declercq ◽  
Gabriel Germain ◽  
...  
Keyword(s):  
Diffraction Analysis ◽  
The Novel ◽  
X Ray Diffraction ◽  
X Ray ◽  
Lycopodium Alkaloid ◽  
New Type

The isolation of the novel pentacyclic base megastachine (1), representative of a new type of Lycopodium alkaloid, is reported. Its structure has been determined by X-ray diffraction analysis.

scholarly journals Reactions of Dihaloboranes with Electron-Rich 1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes

Molecules ◽  
2020 ◽  
Vol 25 (12) ◽  
pp. 2875
Author(s):  
Li Ma ◽  
Xiaolin Zhang ◽  
Wenbo Ming ◽  
Shengxin Su ◽  
Xiaoyong Chang ◽  
...  
Keyword(s):  
Double Bond ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
1H Nmr Spectroscopy ◽  
Variable Temperature ◽  
Organosilicon Compounds ◽  
X Ray Diffraction ◽  
X Ray ◽  
Multinuclear Nmr Spectroscopy ◽  
Bond Character

The reactions of electron-rich organosilicon compounds 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (1), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2), and 1,1′-bis(trimethylsilyl)-1,1′-dihydro-4,4′-bipyridine (12) with B-amino and B-aryl dihaloboranes afforded a series of novel B=N-bond-containing compounds 3–11 and 13. The B=N rotational barriers of 7 (>71.56 kJ/mol), 10 (58.79 kJ/mol), and 13 (58.65 kJ/mol) were determined by variable-temperature 1H-NMR spectroscopy, thus reflecting different degrees of B=N double bond character in the corresponding compounds. In addition, ring external olefin isomers 11 were obtained by a reaction between 2 and DurBBr2. All obtained B=N-containing products were characterized by multinuclear NMR spectroscopy. Compounds 5, 9, 10a, 11, and 13a were also characterized by single-crystal X-ray diffraction analysis.

Carbacylamidophosphates: Synthethis and Structure of N,N'-Tetramethyl-NM-benzoylphosphoryltriamide and Dimorpholido-N-benzoylphosphorylamide

2000 ◽  
Vol 55 (6) ◽  
pp. 495-498 ◽  
Author(s):  
Katerina E. Gubina ◽  
Vladimir A. Ovchynnikov ◽  
Vladimir M. Amirkhanov ◽  
Viktor V. Skopenkoa ◽  
Oleg V. Shishkinb
Keyword(s):  
Nmr Spectroscopy ◽  
Hydrogen Bonds ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hydrogen Atoms ◽  
Sodium Salts ◽  
Space Group ◽  
X Ray ◽  
Centrosymmetric Dimers ◽  
Oxygen Atoms

N,N′-Tetramethyl-N"-benzoylphosphoryltriamide (I) and dimorpholido-N-benzoylphosphorylamide (II), and their sodium salts Nal, Nall were synthesized and characterized by means of IR and 1H, 31P NMR spectroscopy. The structures of I, II were determined by X-ray diffraction: I monoclinic, space group P2i/c with a = 10.162(3), b= 11.469(4), c = 12.286(4) Å , β = 94.04°, V = 1428.4(8) A 3, Z = 4, p(calcd) = 1.187 g/cm3; II monoclinic, space group C2/c with a = 15.503(4), b = 10.991(3), c = 22.000(6) Å, β = 106.39°, V = 3596.3(17) Å3, Z = 8, p(calcd.) = 1.253 g/cm3. The refinement of the structures converged at R = 0.0425 for I, and R = 0.068 for II. In both structures the molecules are connected into centrosymmetric dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups.

Europium(II) Heptaphosphide EuP7 [1] Europium(II)heptaphosphid EuP7 [1]

1980 ◽  
Vol 35 (7) ◽  
pp. 824-831 ◽  
Author(s):  
Hans Georg von Schnering ◽  
Manfred Wittmann
Keyword(s):  
Chair Conformation ◽  
Monoclinic Space Group ◽  
The Novel ◽  
X Ray Diffraction ◽  
X Ray ◽  
Divalent Europium ◽  
Salt Melts ◽  
Tetrahedral Environment ◽  
Mineral Acids ◽  
The Eu

The novel polyphosphide EuP7 was prepared under controlled conditions by the reaction of the elements in salt melts at 750-800 K. EuP7 forms black prismatic crystals not attacked by diluted mineral acids and bases. The thermal decomposition yields EuP3 at 700 K and in further steps EuP2, Eu3P4 and EuP, respectively. According to the crystal structure as well as the electrical, optical and magnetic properties EuP7 is a semiconductor (EG = 0.9 eV; EG (vert) = 1.1 eV) with divalent europium (μ = 7.55 B.M.). The compound crystallizes in the monoclinic space group P21/n with a = 1148.8(7) pm, b = 570.0(3) pm, c = 1061.0(6) pm, and β= 106.08°(5); (X-ray diffraction data; 1479 hkl, R = 0.031). The P-atoms are connected (P-P) = 218.0-223.5 pm) to a 2-dimensional infinite polyanionic structure with homonuclear 3-bonded and 2-bonded P-atoms in the ratio 5:2. The polyanionic network contains P6-rings (chair conformation) as well as P8-rings and P10-rings. The Eu-atoms are bonded to 9 P-atoms (1,4,4-polyhedra) with bond distances ranging from 306.6 to 326.6 pm. The Eu-atoms complete the tetrahedral environment of the P-atoms

1,3,5-Triphosphorinane. Synthese und Struktur der Isomeren des 1,3,5-Triphenyl-1,3,5-triphosphorinans/ 1,3,5-Triphosphorinanes. Synthesis and Structure of the Isomers of 1,3,5-Triphenyl-1,3,5-triphosphorinane

2006 ◽  
Vol 61 (5) ◽  
pp. 577-582 ◽  
Author(s):  
Manfred Fild ◽  
Peter G. Jones ◽  
Michael Lorms ◽  
Stefan Jäger
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Column Chromatography ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The reaction of lithiated Ph(H)PCH2P(H)Ph with (ClCH2)2PPh yields 1,3,5-Triphenyl-1,3,5- triphosphorinane (1) as a mixture of two isomers. The isomers have been separated by column chromatography and characterized by NMR spectroscopy and single crystal X-ray diffraction as the eq-eq-eq (1a) and eq-eq-ax-isomers (1b). (1a) crystallizes with a = 1326.9(3) pm and c = 933.4(3) pm in the rhombohedral space group R3 and displays 3-fold symmetry, showing an eq-eq-eq conformation. (1b) crystallizes in the monoclinic space group P21/c with a = 984.09(12) pm, b = 1757.5(2) pm, c = 1083.13(12) pm, β = 93.329(2)° and displays an ax-eq-eq conformation.

Synthesis, Characterization, and Catalytic Activity of a Series of Aluminium–Amidate Complexes

2015 ◽  
Vol 68 (3) ◽  
pp. 357 ◽  
Author(s):  
Kevin P. Yeagle ◽  
Darryl Hester ◽  
Nicholas A. Piro ◽  
William G. Dougherty ◽  
W. Scott Kassel ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
13C Nmr ◽  
13C Nmr Spectroscopy ◽  
X Ray Diffraction ◽  
Metathesis Reaction ◽  
Chloride Complexes ◽  
1H And 13C Nmr ◽  
X Ray

The aluminium complexes {[κ2-N,O-(t-BuNCOPh)]AlMe2}2 (2), [κ2-N,O-(t-BuNCOPh)]2AlMe (3), and [κ2-N,O-(t-BuNCOPh)]3Al (4) were prepared through the protonolysis reaction between trimethylaluminium and one, two, or three equivalents, respectively, of N-tert-butylbenzamide. Complex 2 was also prepared via a salt metathesis reaction between K(t-BuNCOPh) and dimethylaluminium chloride. Complexes 2–4 were characterized using 1H and 13C NMR spectroscopy. Single-crystal X-ray diffraction analysis of the complexes corroborated ligand : metal stoichiometries and revealed that all the amidate ligands coordinate to the aluminium ion in a κ2 fashion. The Al–amidate complexes 2–4 were viable catalyst precursors for the Meerwein–Ponndorf–Verley–Oppenauer reduction–oxidation manifold, successfully interconverting several classes of carbonyl and alcohol substrates.

Synthesis and Characterization of Tetrakis(pentafluoroethyl)germane

Synthesis ◽  
2017 ◽  
Vol 49 (11) ◽  
pp. 2389-2393 ◽  
Author(s):  
Stefanie Pelzer ◽  
Beate Neumann ◽  
Hans-Georg Stammler ◽  
Nikolai Ignat’ev ◽  
Reint Eujen ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Ir Spectroscopy ◽  
Diffraction Analysis ◽  
Spectroscopic Characterization ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Comprehensive Characterization

This paper describes the synthesis and comprehensive characterization of tetrakis(pentafluoroethyl)germane. In addition to a complete NMR spectroscopic characterization, including the rarely used 73Ge NMR spectroscopy, Ge(C2F5)4 was studied by IR spectroscopy, mass spectrometry as well as X-ray diffraction analysis. A 73Ge NMR investigation as well as an X-ray diffraction study of the related germane Ge(CF3)4 are also included.

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