Phenylsilane dehydrocoupling and addition to styrene catalyzed by (R-indenyl)Ni(phosphine)(methyl) complexes

2009 ◽  
Vol 87 (1) ◽  
pp. 280-287 ◽  
Author(s):  
Yaofeng Chen ◽  
Davit Zargarian
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Variable Temperature ◽  
Structural Parameters ◽  
Catalytic Cycle ◽  
Synthesis And Characterization ◽  
H Nmr ◽  
Solid State Structures ◽  
Indenyl Complexes

This report describes the synthesis and characterization of the Ni–Me complexes (R-indenyl)Ni(PR′3)Me (R = 1-i-Pr, 1-SiMe3, and 1,3-(SiMe3)2; R′= Me, Ph) and outlines their catalytic reactivities in the dehydrogenative oligomerization of PhSiH3 and its addition to styrene in the absence of initiators/activators. Observation of higher hydrosilylation activities for PPh3-based compounds featuring bulky substituents on the indenyl ligand confirms earlier suggestions that phosphine dissociation is an important component of the catalytic cycle for this reaction. In contrast, oligomerization of PhSiH3 is more facile with PMe3-based precursors and independent of the steric bulk of the indenyl ligand, implying that this reaction does not involve phosphine dissociation. These conclusions are consistent with the variable-temperature 1H NMR spectra of {1,3,-(SiMe3)2-indenyl}Ni(PR′3)Me and various structural parameters observed in the solid-state structures of {1,3,-(SiMe3)2-indenyl}Ni(PPh3)Me, {1,3,-(SiMe3)2-indenyl}Ni(PMe3)Cl, and {1-SiMe3-indenyl}Ni(PMe3)Me.Key words: nickel-indenyl complexes, hydrosilylation, hydrosilane oligomerization.

Synthesis and characterization of Pt(II) complexes containing the bidentate pyrazolylgallate ligand, [Me2Gapz2]−

1985 ◽  
Vol 63 (9) ◽  
pp. 2550-2554 ◽  
Author(s):  
Sophia Nussbaum ◽  
Alan Storr
Keyword(s):  
Variable Temperature ◽  
Synthesis And Characterization ◽  
Direct Reaction ◽  
H Nmr ◽  
Nmr Methods

The complexes [Me2Mpz2]Pt(Me)L (where L = CO, Ph3P, or PhC≡CPh for M = Ga; L = PhC≡CPh for M = B) have been synthesized by the direct reaction of the ligands Na[Me2Mpz2] with Pt(Me)Cl(COD) followed by the addition of ligand L. The complexes have been shown to be fluxional in solution by variable temperature 1H nmr methods.

Synthesis and Characterization of FunctionalizedN,N‘-Diphenylformamidinate Silver(I) Dimers:  Solid-State Structures and Solution Properties

1999 ◽  
Vol 38 (24) ◽  
pp. 5571-5578 ◽  
Author(s):  
Stephen J. Archibald ◽  
Nathaniel W. Alcock ◽  
Daryle H. Busch ◽  
David R. Whitcomb
Keyword(s):  
Solid State ◽  
Synthesis And Characterization ◽  
Solution Properties ◽  
Solid State Structures

Iridium(I) complexes containing bidentate pyrazolylgallate ligands. X-ray crystal structures of [Me2Gapz2]Ir(COD), [Ir(μ-pz)(CO)2]2, and [Ir(μ-3,5-Me2pz)(CO)2]2

1985 ◽  
Vol 63 (3) ◽  
pp. 692-702 ◽  
Author(s):  
Sophia Nussbaum ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Crystal Structures ◽  
Variable Temperature ◽  
Hydrogenation Reaction ◽  
Synthesis And Characterization ◽  
Nmr Studies ◽  
X Ray ◽  
H Nmr ◽  
Measurable Activity

The synthesis and characterization of a number of Ir(I) complexes incorporating bidentate, chelating, pyrazolylgallate ligands are described. Non-rigidity for some of the complexes in solution has been demonstrated by variable temperature 1H nmr studies. Crystal structures of three complexes, [Me2Gapz2]Ir(COD), [Ir(μ-pz)(CO)2]2, and [Ir(μ-3,5-Me2pz)(CO)2]2 are reported and confirm the expected boat conformations for the six-membered M—(N—N)2—Ir rings (where M = Ir or Ga) in the compounds. One of the complexes studied has exhibited measurable activity as a catalyst in the hydrogenation reaction of cyclohexene.

scholarly journals Solid-state motion of OTeF5− compounds: detection by 19F NMR and IR spectroscopy and correlation with the X-ray structure of an orthorhombic crystalline modification of [C14H19N2+][OTeF5−] (C14H19N2+ = protonated 1,8-bis(dimethylamino)naphthalene)

1989 ◽  
Vol 67 (11) ◽  
pp. 2023-2029 ◽  
Author(s):  
Patti J. Kellett ◽  
Oren P. Anderson ◽  
Steven H. Strauss ◽  
Kent D. Abney
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Room Temperature ◽  
Variable Temperature ◽  
Structural Parameters ◽  
Crystalline Modification ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Triclinic Modification

An orthorhombic crystalline modification of [(PS)H+][OTeF5−] was studied by single crystal X-ray diffraction ((PS)H+ = protonated 1,8-bis(dimethylamino)naphthalene): orthorhombic, space group Cmcm, a = 8.607(2), b = 14.048(3), c = 13.365(2) Å, Z = 4, T = −130 °C. The structural parameters for the anion and cation in this modification (Mod-B) are very similar to those for the previously reported triclinic modification of this salt (Mod-A). However, variable temperature IR spectra for Mod-B suggest that the OTeF5− anion is exhibiting a two-site O/Fax interchange above −70 °C. Solid-state 19F NMR spectra suggest that this interchange may be as rapid as 104–105 s−1 at room temperature. Keywords: crystal structure of protonated 1,8-bis(dimethylamino)naphthalene)pentafluorotellurate(VI), polymorphism, solid state 19FNMR.

scholarly journals Synthesis and characterization of pentanuclear Fe–Ir carbonyl clusters. Solid-state structures of [N(PPh3)2]2[FeIr4(CO)15] and [PPh4][Fe2Ir3(CO)14]

1989 ◽  
pp. 1109-1116 ◽  
Author(s):  
Roerto Dalla Pergola ◽  
Luigi Garlaschelli ◽  
Francesco Demartin ◽  
Mario Manassero ◽  
Norberto Masciocchi ◽  
...  
Keyword(s):  
Solid State ◽  
Synthesis And Characterization ◽  
Carbonyl Clusters ◽  
Solid State Structures

Synthesis and characterization of cationic iron complexes supported by the neutral ligands NPi-Pr3, NArPi-Pr3, and NSt-Bu3

2005 ◽  
Vol 83 (4) ◽  
pp. 332-340 ◽  
Author(s):  
Cora E MacBeth ◽  
Seth B Harkins ◽  
Jonas C Peters
Keyword(s):  
Solid State ◽  
Bond Distance ◽  
Iron Complexes ◽  
Synthesis And Characterization ◽  
Epr Spectrum ◽  
Chloride Complexes ◽  
Bipyramidal Structure ◽  
Neutral Ligands ◽  
Solid State Structures

This paper compares the local geometries, spin states, and redox properties of a series of iron complexes supported by neutral, tetradentate NP3 (tris(phosphine)amine) and NS3 (tris(thioether)amine) ligands. Our consideration of an Fe-mediated N2 fixation scheme similar to that proposed by Chatt for molybdenum motivates our interest in systems of these types. This report specifically describes the synthesis and characterization of cationic Fe(II) chloride complexes supported by the neutral ligands NPi-Pr3 (NPi-Pr3 = [N(CH2CH2P-i-Pr2)3]), NArPi-Pr3 (NArPi-Pr3 = [N(2-diisopropylphosphine-4-methylphenyl)3]), and NSt-Bu3 (NSt-Bu3 = [N(CH2CH2S-t-Bu)3]). The solid-state structures, electrochemistry, and magnetic properties of these complexes are reported. Whereas the NPi-Pr3 and NArPi-Pr3 ligands provide pseudotetrahedral S = 2 ferrous cations [Fe(NPi-Pr3)Cl]PF6 (1[PF6]) and [Fe(NArPi-Pr3)Cl]BPh4 (2[BPh4]) featuring a long Fe—N bond distance, the NSt-Bu3 ligand gives rise to a trigonal bipyramidal structure with a S = 1 ground state and a much shorter Fe–N interaction. The complexes 1[BPh4] and 2[BPh4] can be reduced under CO to give rise to the five-coordinate Fe(I) monocarbonyls [Fe(NPi-Pr3)CO]BPh4 (4[BPh4]) and [Fe(NArPi-Pr3)CO]BPh4 (5[BPh4]). The solid-state structures and electrochemistry of 4[BPh4] and 5[BPh4] are described, as is the EPR spectrum of 4[BPh4]. The synthesis and characterization of the hydride–dinitrogen complex [Fe(NPi-Pr3)(N2)(H)]PF6 (6[PF6]) has also been accomplished and its properties are also reported.Key words: nitrogenase, iron, polydentate phosphines, thioether ligands, N2 chemistry, nitrogen, Fe(I).

scholarly journals Synthesis and characterization of π–extended “earring” subporphyrins

2018 ◽  
Vol 14 ◽  
pp. 1956-1960 ◽  
Author(s):  
Haiyan Guan ◽  
Mingbo Zhou ◽  
Bangshao Yin ◽  
Ling Xu ◽  
Jianxin Song
Keyword(s):  
Single Crystal ◽  
Aromatic Ring ◽  
Nmr Spectra ◽  
Ring Current ◽  
Synthesis And Characterization ◽  
Single Crystal Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Single Crystal Structures

A π-extended “earring” subporphyrin 3 was synthesized from β,β′-diiodosubporphyrin and diboryltripyrrane via a Suzuki–Miyaura coupling and following oxidation. Its Pd complex 3Pd was also synthesized and both of the compounds were fully characterized by 1H NMR, MS and X-ray single crystal diffraction. The 1H NMR spectra and single crystal structures revealed that aromatic ring current did not extend to the “ear” in both of the two compounds. Their UV–vis/NIR spectra were recorded and the absorption of both compounds is extended to the NIR region and that the absorption of 3Pd is further red-shifted and more intense.

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