The life, death, and ROMP activity of ruthenium complexes containing the basic, chelating diphosphine bis(dicyclohexyl)-1,4-phosphinobutane

2001 ◽  
Vol 79 (5-6) ◽  
pp. 958-963 ◽  
Author(s):  
Dino Amoroso ◽  
Glenn PA Yap ◽  
Deryn E Fogg
Keyword(s):  
Crystal Structure ◽  
Key Words ◽  
Ring Opening ◽  
Chlorinated Solvents ◽  
Metathesis Polymerization ◽  
Space Group ◽  
X Ray ◽  
Vacuum Atmosphere ◽  
Benzylidene Derivative

Reaction of RuCl2(PPh3)3 with bis(dicyclohexyl)-1,4-phosphinobutane (dcypb) under N2 affords access to a formerly elusive family of dcypb complexes based on the RuCl2(PP) core. Under Ar or vacuum atmosphere, decomposition occurs via Ru-promoted dehydrogenation of the dcypb ligand. While the N2-stabilized species [RuCl2(dcypb)]2(N2) (4a) is easily handled under N2 in nonchlorinated solvents, reaction with chlorinated solvents rapidly yields paramagnetic Ru2Cl5(dcypb)2 (5). The N2 ligand within 4a is readily displaced under H2 or CO atmosphere, yielding Ru2Cl4(dcypb)2(H2) (6) or RuCl2(dcypb)(CO)2, the latter as a mixture of ccc-(7) and tcc-(8) isomers. Benzylidene derivative RuCl2(dcypb)(CHPh) (1a), prepared in situ by reaction of 4a with PhCHN2, proves exceptionally active in ring-opening metathesis polymerization (ROMP) of norbornene. The X-ray crystal structure of 5 is reported: triclinic, a = 13.390(2), b = 15.726(2), c = 19.524(2) Å, α = 77.325(2), β = 70.964(2), γ = 73.478(2)°, with space group P[Formula: see text] and Z = 2.Key words: ruthenium, alkylphosphine, dehydrogenation, carbene, metathesis, crystal structure.

The selective complexation of adamantane nitriles by tungsten pentacarbonyl

1996 ◽  
Vol 74 (1) ◽  
pp. 107-113 ◽  
Author(s):  
Valerie J. Jefford ◽  
Melbourne J. Schriver ◽  
Michael J. Zaworotko
Keyword(s):  
Crystal Structure ◽  
Key Words ◽  
Crystal Data ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Pure Compounds ◽  
Semi Empirical ◽  
Oxygen Atoms ◽  
Selective Complexation

Adamantyl-1,3,4-oxathiazol-2-one is usually prepared as a mixture with 1-adamantanecarbonitrile. To separate these two compounds the mixture is reacted with thf•W(CO)5, which selectively forms a complex with the nitrile. The resulting mixture can then be readily separated into pure compounds by sublimation. Characterization data are presented, including the X-ray crystal structure of the nitrile complex, which can be prepared directly from the reaction of the adamantyl nitrile and thf•W(CO)5. (Crystal data for C16H15NO5W: orthorhombic, space group Pmcn, a = 10.5869(19) Å, b = 14.0622(22) Å, c = 23.342(4) Å, V = 3475.0(11) Å, Z = 8, R = 0.042.) The nitrile can be recovered from the complex by reaction with P(C6H5)3 followed with separation by sublimation. The reaction of the related 1-cyano-3-(1,3,4-oxathiazol-2-on-5-yl)-adamantane with thf•W(CO)5 yields a complex in which the site of coordination is shown spectroscopically to be the nitrile moiety. Semi-empirical calculations at the PM3 level indicate that the oxathiazolone heterocycle may be a poor ligand due to the influence of the exo- and endo-cyclic oxygen atoms. Key words: oxathiazolone, nitrile, tungsten, complexation, selectivity, adamantane.not available

Synthesis, characterization, and reactivity of a ruthenium(II) N,N′,N″-tris(2-pyridyl)phosphine complex. X-ray analysis of RuCl2(PPh3)(Ppy3) (py = 2-pyridyl)

1996 ◽  
Vol 74 (11) ◽  
pp. 2064-2072 ◽  
Author(s):  
Richard P. Schutte ◽  
Steven J. Rettig ◽  
Brian R. James
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Key Words ◽  
Phosphorus Atom ◽  
Electron Donors ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Phosphine Complex

Reaction of RuCl2(PPh3)3 with Ppy3 (py = 2-pyridyl) in benzene produced the N,N′,N″-Ppy3 complex RuCl2(PPh3)(Ppy3) 1. Crystals of RuCl2(PPh3)(Ppy3)•2CH2Cl2 (C35H31Cl6N3P2Ru) are monoclinic, a = 17.269(2), b = 10.797(1), c = 20.604(1) Å, β = 107.461(6)°, Z = 4, space group P21/c. The structure was solved by the Patterson method and was refined by full-matrix least-squares procedures to R = 0.039 and Rw = 0.035 for 4184 reflections with I ≥ 3σ(I). Complex 1 reacts in MeOH or benzene with two-electron donors (L) to give the chloride-substituted, [RuCl(L)(PPh3)(Ppy3)]PF6, or the triphenylphosphine-substituted products, RuCl2(L)(Ppy3), (L = CO, MeCN, PhCN), respectively. [RuCl(MeOH)(PPh3)(Ppy3)]BPh4 was also isolated. The non-coordinated phosphorus atom in 1 was oxidized to form RuCl2(PPh3)(OPpy3). Key words: ruthenium, pyridylphosphines, crystal structure

scholarly journals DIBUTYLTIN(IV) ALKYLCYCLOHEXYLDITHIOCARBAMATES: SPECTROSCOPIC CHARACTERIZATION AND CRYSTAL STRUCTURES OF DIBUTYLTIN(IV) N-METHYL AND N-ETHYLCYCLOHEXYLDITHIOCARBAMATE

2017 ◽  
Vol 25 (2) ◽  
pp. 419-426
Author(s):  
Normah Awang ◽  
Ibrahim Baba ◽  
Y. Farina Abd. Aziz ◽  
Bohari M. Yamin
Keyword(s):  
Crystal Structure ◽  
Nmr Spectroscopy ◽  
13C Nmr ◽  
13C Nmr Spectroscopy ◽  
Spectroscopic Characterization ◽  
Monoclinic System ◽  
Space Group ◽  
X Ray ◽  
In Situ Method

A new series of dibutyltin(IV) alkylcyclohexyldithiocarbamates of the type (C4H9)2Sn[S2CNR(C6H11)]2 (R = CH3, C2H5, i-C3H7) have been successfully synthesized using in-situ method. These compounds were characterized by elemental analysis, infrared and 13C NMR spectroscopy. A single crystal X-ray analysis of dibutyltin(IV) ethylcyclohexyldithiocarbamate, (C4H9)2Sn[S2CN(C2H5)(C6H11)]2 (compound 2) showed that the system of this crystal is triclinic with space group P-1 while dibutyltin(IV) methylcyclohexyldithiocarbamate, (C4H9)2Sn[S2CN(CH3)(C6H11)]2 (compound 1) has monoclinic system and it’s space group is P21/c. In the crystal structure of compound 2, the dithiocarbamate ligands are bidentically chelated to the tin atom with non-equivalent of the Sn-S distances: Sn(1)-S(1) = 2.9255(11) and Sn(1)-S(2) = 2.5419(10); Sn(1)-S(3) = 2.8922(9) and Sn(1)-S(4) = 2.5293(10) Å while in compound 1, the dithiocarbamate ligands were anisobidentically  chelated to the tin atom.       

A novel coordination mode for a pyridylphosphine ligand. X-ray structures of [RuCl2(NO)L] (I) and [RuCl2(NO)L]·DMSO (II) (L = [(2-py)2PC2H4POO(2-py)2]-)

2001 ◽  
Vol 79 (5-6) ◽  
pp. 1030-1035 ◽  
Author(s):  
Alzir A Batista ◽  
Salete L Queiroz ◽  
Peter C Healy ◽  
Robbie W Buckley ◽  
Sue E Boyd ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Key Words ◽  
Coordination Mode ◽  
Ruthenium Complex ◽  
Distorted Octahedron ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Ruthenium Atom ◽  
Bonding Mode

The ruthenium(II) complex, [RuCl2(NO)L] (I), (L = [(2-py)2PC2H4PO2(2-py)]-) was obtained from recrystallization of RuCl3NO(d2pype) (d2pype = (2-py)2PC2H4P(2-py)2) in the presence of HNO3, crystallizing in the monoclinic space group P21 (no. 4), with a = 8.012(4) Å, b = 14.454(4) Å, c = 9.353(3) Å, β = 105.77(3)°, and Z = 2. Crystals of the DMSO solvate of the complex (II) were obtained from (CD3)2SO solution, crystallizing in the monoclinic space group P21/c (no.14) with a = 9.7080(2) Å, b = 22.2920(5) Å, c = 11.5230(3) Å, β = 92.0450(10)°, and Z = 4. In both complexes, the geometry about the ruthenium atom is a distorted octahedron mainly as a result of the tridentate [P,N,O]-bonding mode of L. The ν (NO) bands at 1875 cm–1 in both complexes are consistent with the linear disposition of the NO group and the Ru atom as is observed in the X-ray crystal structure (Ru-N1-O1 angle = 178.5(4)°).Key words: pyridylphosphine, nitrosyl, ruthenium complex, X-ray structure.

Ternary cobalt germanium pnictides CoGexPn1-x (Pn = P, As, Sb) and the structure of Co3Ge2Sb, an intermetallic compound with stuffed Sb2 pairs

1998 ◽  
Vol 76 (11) ◽  
pp. 1588-1594 ◽  
Author(s):  
Allison M Mills ◽  
Robert Lam ◽  
Arthur Mar
Keyword(s):  
Crystal Structure ◽  
Intermetallic Compound ◽  
Single Crystal ◽  
Key Words ◽  
Intermediate Structure ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The ternary cobalt germanium pnictide systems CoGexPn1-x (Pn = P, As, Sb; 0 <x <1) were investigated. The ternary phosphides CoGexP1-x and arsenides CoGexAs1-x adopt the MnP structure (Pnma) in the range 0 <x <0.8, with Ge and Pn (Pn = P, As) disordering over the anion sites. Reactions in the antimonide system CoGexSb1-x result in a mixture of ternary phases, one with the NiAs structure (P63/mmm) in which Ge and Sb disorder over the anion sites, and another that is a new intermetallic compound, Co3Ge2Sb. Single-crystal X-ray diffraction reveals that Co3Ge2Sb crystallizes in the hexagonal space group P6/mmm with a = 8.9128(13) Å, c = 7.6312(8) Å, and Z = 6 (T = 22°C). The structure of Co3Ge2Sb comprises alternating kagomé nets of Co atoms and 63 nets of Ge atoms, with Sb2 pairs stuffed along the centres of the concentric hexagons of these nets. Co3Ge2Sb may be regarded as an intermediate structure that is distorted from the limiting CoSn and CaCu5 structures. Key words: cobalt, germanium, antimony, pnictide, crystal structure

Preparation of Cr2(CO)8(NO)2 and X-ray crystal structures of Cr2(CO)8(NO)2 and Cr2(CO)9NO−. Stereochemical comparisons to Cr2(CO)102−

1991 ◽  
Vol 69 (12) ◽  
pp. 2136-2141 ◽  
Author(s):  
A. P. Masters ◽  
M. Parvez ◽  
T. S. Sorensen
Keyword(s):  
Crystal Structure ◽  
Bond Length ◽  
Key Words ◽  
Crystal Structures ◽  
Quantitative Yield ◽  
Space Group ◽  
X Ray ◽  
Metal Metal ◽  
Chromium Carbonyl ◽  
The One

Cr2(CO)8(NO)2 (1) has been prepared and characterized, and the crystal structure determined, along with that of the related salt Cr2(CO)9NO− monoanion (2) as the CH2Cl2-solvated PPN+ salt (where PPN+ denotes the (PPh3)2N+ monocation). Both 1 and 2 possess a metal–metal bonded structure analogous to that of Mn2(CO)10 and the electronically equivalent Cr2(CO)102− dianion. Although Cr2(CO)8(NO)2 (1) is slowly formed in poor yield from Cr(CO)4NO− and Cr(CO)4NOBr, it can be prepared in an almost quantitative yield by the one-electron oxidation of the monoanion with trityl hexafluorophosphate. The slowness of the former reaction makes Cr(CO)4NO− useful as a two-electron reductant of organohalide bonds. Triclinic crystals of 1 incorporate two distinct molecules in die [Formula: see text] space group, although the geometries of each are almost identical. Triclinic crystals of monoanion (2) also belong to the [Formula: see text] space group. The Cr—Cr bond length is 3.00–3.02 Å in 1 and 2.995 Å in 2, compared to 2.904 Å for the central Mn—Mn bond in Mn2(CO)10. Key words: chromium nitrosyl, chromium carbonyl, X-ray crystal structure, metalate anion, metal–metal dimer.

About the air- and water-stable copper(I) dicyanamide: synthesis, crystal structure, vibrational spectra and DSC/TG analysis of Cu[N(CN)2]

2017 ◽  
Vol 72 (2) ◽  
pp. 159-165 ◽  
Author(s):  
Olaf Reckeweg ◽  
Robert E. Dinnebier ◽  
Armin Schulz ◽  
Björn Blaschkowski ◽  
Christof Schneck ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Vibrational Spectra ◽  
Lattice Parameters ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Tg Analysis ◽  
Space Group ◽  
X Ray ◽  
Light Yellow

AbstractLight-yellow microcrystalline samples of Cu[dca] ([dca]−≡[N(CN)2]−≡dicyanamide anion) were obtained by blending an in-situ generated aqueous Cu+ brine with stoichiometric amounts of Na[dca] dissolved in water. The crystal structure of Cu[dca] was solved and refined from powder X-ray diffraction (PXRD) data. Cu[dca] crystallizes in the orthorhombic space group Cmcm (no. 63) with the lattice parameters of a=356.28(3), b=611.10(9) and c=1525.87(10) pm. The crystal structure contains undulated chains of alternating Cu+ and boomerang-shaped [N≡C–N–C≡N]− ions with C2v symmetry running along [100]. It is closely related to that of Ag[dca] crystallizing in space group Pnma (no. 62). The vibrational spectra for Cu[dca] and Cu[dca]2 were recorded exhibiting modes typical for the dicyanamide anion. Comparative DSC/TG measurements were performed for both copper dicyanamides and the cyanide Cu[CN].

The preparation of 1,2,3,5-dithiadiazolium chlorides from the reaction of nitrile sulphides with thiazyl chloride

1994 ◽  
Vol 72 (4) ◽  
pp. 1143-1153 ◽  
Author(s):  
John N. Bridson ◽  
Steven B. Copp ◽  
Melbourne J. Schriver ◽  
Shuguang Zhu ◽  
Michael J. Zaworotko
Keyword(s):  
Crystal Structure ◽  
Cycloaddition Reaction ◽  
Heterocyclic Ring ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
Space Group ◽  
X Ray ◽  
Alkyl Derivatives ◽  
First Time

Adamantyl-1,3,4-oxathiazol-2-one has been prepared for the first time and from it 1-adamantyl nitrile sulphide has been generated. Characterisation data are presented, including the X-Ray crystal structure of the oxathiazolone. (Crystal data for C12H15NO2S: monoclinic, space group P21/c, a = 11.334(2) Å,b = 7.344(1) Å, c = 14.373(2) Å,β = 107.74(1)°, V = 1139.5(3) Å3, Z = 4, R = 0.042). The planar heterocyclic ring is similar to structures observed in the gas phase for other oxathiazolone derivatives. The nitrile sulphide was reacted with dimethyl-acetylene dicarboxylate in situ to give an isothiazole derivative. The X-Ray crystal structure of 3-adamantyl-4,5-bis(methoxycarbonyl)-isothiazole has been obtained. (Crystal data for C17H21NO4S: monoclinic, space group P21/n, a = 7.305(4) Å, b = 7.339(4) Å, c = 31.552(4) Å, β = 92.75(3)°, V = 1690(1) Å3, Z = 4, R = 0.079). A general cycloaddition reaction was discovered between the nitrile sulphides and thiazyl chloride to give 1,2,3,5-dithiadiazolium chlorides. The structure of the new 4-adamantyl-1,2,3,5-dithiadiazolium chloride was confirmed by reduction to the 4-adamantyl-1,2,3,5-dithiadiazolyl for which the X-Ray crystal structure has been determined. (Crystal data for C11H15N2S2: monoclinic, space group C2, a = 10.284(4) Å, b = 8.651(2) Å, c = 13.669(2) Å, β = 112.83(1)°, V = 1120.9(4) Å3, Z = 4, R = 0.042). The radical adopts a twisted dimer structure in the solid state which is similar to the structures observed for other alkyl derivatives.

Spectroscopic and crystallographic studies of phosphino adducts of indium(III) iodide

1996 ◽  
Vol 74 (8) ◽  
pp. 1535-1549 ◽  
Author(s):  
Martyn A. Brown ◽  
Dennis G. Tuck ◽  
Edward J. Wells
Keyword(s):  
Crystal Structure ◽  
Coordination Chemistry ◽  
Solid State ◽  
Key Words ◽  
Solution Phase ◽  
Reaction Conditions ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Complete Dissociation

Indium(III) iodide forms both 1:1 and 1:2 adducts with triphenylphosphine, depending on the reaction conditions, and especially on the solvent used. The complex InI3•PPh3 involves four-coordination at indium; the structure is trigonal, with a = 15.105(4) Å, c = 16.769(7) Å, V = 3313(2) Å3, Z = 6, and space group [Formula: see text]. Crystals were also obtained in which InI3•PPh3 and InI3(PPh3)2 are present in a 1:1 ratio; these are also trigonal, a = 15.473(4) Å, c = 41.701(7) Å, V = 8646.1(1.8) Å3,Z = 3 + 3 and space group [Formula: see text]. The 1:2 adduct has approximately D3h symmetry in the InI3P2 kernel. The bond distances and angles are discussed; in particular, the In—P bonds are extremely weak in the 1:2 adduct. This compound has been shown by 31P NMR to undergo complete dissociation in solution to InI3•PPh3 and PPh3. The addition of R4NI (R = n-C3H7, n-C4H9) causes quantitative conversion to InI4− and free Ph3P. Similar experiments are reported for the compound InI3(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane), whose structure is an infinite chain of InI3 units linked through In-P-C2H4-P-In coordination. The crystal structure showed that InI3(dppe) cocrystallizes with an equimolar quantity of dppe; these crystals are cubic, a = 41.445(14) Å, b = 15.944(8) Å, c = 16.533(11) Å, p = 102.02(4)°, V = 10 685(9) Å3, Z = 4 + 4, space group C2/c, Solid state and solution phase results are discussed in terms of the coordination chemistry of indium(III). Key words: indium, phosphorus, coordination chemistry, multinuclear NMR, X-ray crystallography.

Porphyrins incorporating heterocyclic N-oxides: (oxidopyridyl)porphyrins, porphyrin-N-oxides, and a tirapazamine-porphyrin conjugate

1999 ◽  
Vol 77 (2) ◽  
pp. 182-198 ◽  
Author(s):  
Jeffrey J Posakony ◽  
Russell C Pratt ◽  
Steven J Rettig ◽  
Brian R James ◽  
Kirsten A Skov
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Key Words ◽  
Direct Methods ◽  
Spectroscopic Methods ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

Porphyrins containing one to four 4-pyridyl groups as meso-substituents were synthesized via a mixed aldehyde condensation, and then "N-oxidized" with m-chloroperbenzoic acid to produce five novel (oxidopyridyl) porphyrins and seven porphyrin-N-oxides, which were characterized by analysis and spectroscopic methods, especially NMR; an X-ray crystal structure of 5-(1-oxido-4-pyridyl)-10,15,20-triphenylporphyrin was also obtained. Crystals of (oxidopyridyl)triphenylporphyrin are tetragonal, a = b = 15.174(1), c = 13.709(1) Å, Z = 4, space group I2d. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R = 0.031 (Rw = 0.026) for 685 reflections with I [Formula: see text] 3σ(I). Sulfonation of two of the (oxidopyridyl)porphyrins was achieved readily with no loss of oxygen from the oxidopyridyl groups. Tirapazamine (3-amino-1,2,4-benzotriazine-1,4-di-N-oxide) was treated with triphosgene to yield the previously reported 2H-[1,2,4]oxadiazolo[3,2-c][1,2,4]benzotriazin-2-one-5-oxide (1); this reacts like an isocyanate and with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin yields a tirapazamine-porphyrin conjugate (2).Key words: porphyrin-N-oxides, (oxidopyridyl)porphyrins, tirapazamine.

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