Coordination Chemistry of Mercury-Containing Anticrowns. Complexation of Perfluoro-o,o′-biphenylenemercury with o-Xylene and Acetonitrile and the First X-ray Diffraction Evidence for Its Trimeric Structure

2015 ◽  
Vol 34 (8) ◽  
pp. 1530-1537 ◽  
Author(s):  
Kirill I. Tugashov ◽  
Dmitry A. Gribanyov ◽  
Fedor M. Dolgushin ◽  
Alexander F. Smol’yakov ◽  
Alexander S. Peregudov ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
X Ray Diffraction ◽  
X Ray ◽  
Trimeric Structure

scholarly journals A Versatile Approach to Access Trimetallic Complexes Based on Trisphosphinite Ligands

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 593
Author(s):  
Juan Miranda-Pizarro ◽  
Macarena G. Alférez ◽  
M. Dolores Fernández-Martínez ◽  
Eleuterio Álvarez ◽  
Celia Maya ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
Late Transition Metal ◽  
X Ray Diffraction ◽  
X Ray ◽  
Full Characterization ◽  
Metal Precursors ◽  
Straightforward Method ◽  
One Step ◽  
Late Transition

A straightforward method for the preparation of trisphosphinite ligands in one step, using only commercially available reagents (1,1,1-tris(4-hydroxyphenyl)ethane and chlorophosphines) is described. We have made use of this approach to prepare a small family of four trisphosphinite ligands of formula [CH3C{(C6H4OR2)3], where R stands for Ph (1a), Xyl (1b, Xyl = 2,6-Me2-C6H3), iPr (1c), and Cy (1d). These polyfunctional phosphinites allowed us to investigate their coordination chemistry towards a range of late transition metal precursors. As such, we report here the isolation and full characterization of a number of Au(I), Ag(I), Cu(I), Ir(III), Rh(III) and Ru(II) homotrimetallic complexes, including the structural characterization by X-ray diffraction studies of six of these compounds. We have observed that the flexibility of these trisphosphinites enables a variety of conformations for the different trimetallic species.

scholarly journals An N4-Tetradentate Hydrazone Ligand That Binds in a Neutral, Mono- and Bisdeprotonated Form to Iron(II) and Zinc(II) Metal Ions

Crystals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 982
Author(s):  
Devaraj Pandiarajan ◽  
Thomas Fox ◽  
Bernhard Spingler
Keyword(s):  
Mass Spectrometry ◽  
Coordination Chemistry ◽  
Transition Metals ◽  
Metal Ions ◽  
Elemental Analysis ◽  
X Ray Diffraction ◽  
Hydrazone Ligand ◽  
X Ray

The coordination chemistry of butane-2,3-dione bis (2′-pyridylhydrazone) towards the divalent first-row transition metals zinc and iron has been explored. Depending upon the conditions, the ligand in the six complexes was found to be either neutral, mono, or doubly deprotonated. The zinc(II) and iron(II) complexes were fully characterized by elemental analysis, mass spectrometry, and X-ray diffraction methods.

Synthesis and coordination chemistry of silver(I), gold(I) and gold(III) complexes with picoline-functionalized benzimidazolin-2-ylidene ligands

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Mareike C. Jahnke ◽  
F. Ekkehardt Hahn
Keyword(s):  
Coordination Chemistry ◽  
Silver Oxide ◽  
Lithium Bromide ◽  
Metal Center ◽  
Molecular Structures ◽  
Transfer Reactions ◽  
Silver Complexes ◽  
X Ray Diffraction ◽  
X Ray ◽  
Halide Exchange

Abstract The reactions of N-alkyl-N′-picolyl-benzimidazolium bromides or N,N′-dipicolyl-benzimidazolium bromide with silver oxide yielded the silver dicarbene complexes of the type [Ag(NHC)2][AgBr2] 1–4 (NHC = picoline-functionalized benzimidazolin-2-ylidene). The silver complexes 1–4 have been used in carbene transfer reactions to yield the gold(I) complexes of the type [AuCl(NHC)] 5–8 in good yields. A halide exchange at the metal center of complexes 5–8 with lithium bromide yielded the gold bromide complexes 9–12. Finally, the oxidation of the gold(I) centers in complexes 9–12 with elemental bromine gave the gold(III) complexes of the type [AuBr3(NHC)] 13–16. Molecular structures of selected Au(I) and Au(III) complexes have been determined by X-ray diffraction studies.

Pyrrole Thioaldehyde Complexes of Nickel, Palladium and Platinum

2004 ◽  
Vol 59 (11-12) ◽  
pp. 1372-1378 ◽  
Author(s):  
Peter J. Pogorzeleca ◽  
David H. Reid ◽  
Derek A. Tocher ◽  
James D. E. T. Wilton-Ely
Keyword(s):  
Coordination Chemistry ◽  
X Ray Diffraction ◽  
X Ray

The coordination chemistry of the unusual, pyrrole-stabilised thioaldehyde molecules, 3,5-dimethylpyrrole-2-carbothioaldehyde (HSPyMeHMe) and 3,5-dimethyl-4-ethylpyrrole-2-carbothioaldehyde (HSPyMeEtMe) has been investigated with nickel, palladium and platinum in the complexes [M(κ2- SPyMeRMe)2] (M = Ni, Pd, Pt; R = H, Et). The structure of the cyclometallated derivative [Pd(η2- C,N-C6H4CH2NMe2)(κ2-SPyMeEtMe)] was determined by X-ray diffraction.

Synthese und Koordinationschemie eines neuartigen Bistetrazols: Ein 1D-Metallopolymer durch Selbstorganisation koordinativ ungesättigter Zink(II)-M4onomere [1] / Synthesis and Coordination Chemistry of a New Bistetrazole: A 1D-Metallopolymer via Self-Assembly of Monomeric Zinc(II)-Buildingblocks

1995 ◽  
Vol 50 (4) ◽  
pp. 642-648 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Klaus Schobert ◽  
Stefan Trümmer ◽  
Alexander Wolski
Keyword(s):  
Coordination Chemistry ◽  
Self Assembly ◽  
Intermediate Formation ◽  
The Self ◽  
Polymeric Chain ◽  
X Ray Diffraction ◽  
Bridging Ligands ◽  
Subsequent Formation ◽  
X Ray ◽  
Polymeric Compounds

The new bistetrazole 13 has been obtained by subsequent formation of the two heterocyclic units. In methanolic solution 13 reacts with zinc(II) acetate to yield the pseudo-meso-1 D-coordination polymer [ZnL2(MeOH)]n (n = ∞) 14. The structure of 14 was established by single crystal X-ray diffraction. The generation of the polymeric chain 14 is understandable, if intermediate formation of coordinatively unsaturated zinc(II) buildingblocks (Δ)-15 and (Λ)-15 is assumed. Alternating linkage of the self-complementary chiral monomers 15, across one cyanofunction each, leads to 14 with zinc being essentially octahedrally coordinated. Compared with polymeric compounds of similar bridging ligands, the Zn ··· N≡C-distance in 14 (225,7 pm) is short.

Molecular structures of tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium

2016 ◽  
Vol 72 (11) ◽  
pp. 806-812 ◽  
Author(s):  
Yi Rong ◽  
David Sambade ◽  
Gerard Parkin
Keyword(s):  
Coordination Chemistry ◽  
Olefin Polymerization ◽  
Metal Center ◽  
Molecular Structures ◽  
Direct Influence ◽  
X Ray Diffraction ◽  
X Ray ◽  
Polymerization Catalysis ◽  
Sterically Demanding ◽  
Titanium Zirconium

Cyclopentadienyl and tris(pyrazolyl)hydroborate have found much use as supporting ligands in the chemistry of titanium, zirconium and hafnium, especially with respect to applications involving olefin polymerization catalysis. In contrast, closely related tris(1-alkyl-2-mercaptoimidazolyl)hydroborate, [TmR], ligands have so far found little application to the chemistry of these elements, despite the fact that such ligands are currently used extensively in coordination chemistry. In view of the fact that a substituent in the 2-position exerts a direct influence on the steric environment of the metal center, we report here the application of the sterically demanding tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate [Tm^{{\rm Bu}^{\rm t}}] ligand to these metals. Dichlorido(η5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]zirconium(IV) benzene hemisolvate, [Zr(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (I), dichlorido(η5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]titanium(IV) benzene hemisolvate, [Ti(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (II), [bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]dichlorido(η5-cyclopentadienyl)zirconium(IV), [Zr(C14H24BN4S2)(C5H5)Cl2], (III), (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ2N3,S)dichlorido(η5-cyclopentadienyl)zirconium(IV) benzene monosolvate, [Zr(C7H11N2S)(C7H12N2S)(C5H5)Cl2]·C6H6, (IV), and tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,S′′]hafnium(IV) benzene tetrasolvate, [Hf(C7H7)3(C21H34BN6S3)]·4C6H6, (V), have been structurally characterized by X-ray diffraction. The [Tm^{{\rm Bu}^{\rm t}}^{{\rm Bu}^{\rm t}}] ligand coordinates to Ti and Zr in Cp[κ3S2,H-Tm^{{\rm Bu}^{\rm t}}]MCl2[M = Zr, (I), and Ti, (II)] in a κ3S2,Hmode, while the benzyl compounds [Tm^{{\rm Bu}^{\rm t}}]M(CH2Ph)3[M = Zr and Hf, (V)] exhibit κ3S3coordination.

scholarly journals Two Beta-Phosphorylamide Compounds as Ligands for Sm3+, Eu3+, and Tb3+: X-ray Crystallography and Luminescence Properties

Molecules ◽  
2020 ◽  
Vol 25 (13) ◽  
pp. 2971
Author(s):  
Alan R. Lear ◽  
Jonah Lenters ◽  
Michael G. Patterson ◽  
Richard J. Staples ◽  
Eric J. Werner ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
Solid State ◽  
Luminescence Properties ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Lifetime Decay ◽  
Oxygen Atoms

This paper describes the synthesis of two beta-phosphorylamide ligands and their coordination chemistry with the Ln ions Tb3+, Eu3+, and Sm3+. Both the ligands and Ln complexes were characterized by IR, NMR, MS, and X-ray crystallography. The luminescence properties of the Tb3+ and Eu3+ complexes were also characterized, including the acquisition of lifetime decay curves. In the solid state, the Tb3+ and Sm3+ ligand complexes were found to have a 2:2 stoichiometry when analyzed by X-ray diffraction. In these structures, the Ln ion was bound by both oxygen atoms of each beta-phosphorylamide moiety of the ligands. The Tb3+ and Eu3+ complexes were modestly emissive as solutions in acetonitrile, with lifetime values that fell within typical ranges.

Coordination Chemistry of Polynitriles, I. Syntheses and Crystal Structures of [Ag(PCC)(DMF)], [Ni(DMF)6](PCC)2 and [Co(DMF)6](PCC)2 (PCC = [C5(CN)5]-, DMF = N,N-Dimethylformamide) [1]

2013 ◽  
Vol 68 (5-6) ◽  
pp. 546-550 ◽  
Author(s):  
Karlheinz Sünkel ◽  
Dietmar Reimann
Keyword(s):  
Coordination Chemistry ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Pentagonal Symmetry

Recrystallization of silver pentacyanocyclopentadienide Ag[C5(CN)5] from N,N-dimethylformamide (DMF) gives the polymeric 1:1 complex [Ag{C5(CN)5}(DMF)] (1). The Ag+ cation is coordinated by three N atoms of three different [C5(CN)5]- anions and two O atoms of two DMF molecules. Each [C5(CN)5]- is coordinated via three neighboring CN groups to three different Ag+ ions, while each DMF molecule bridges two Ag+ ions via its O atom. Treatment of NiCl2 6H2O, CoCl2 6H2O or ZnCl2 with Ag[C5(CN)5] in DMF gives the DMF complexes [M(DMF)6][C5(CN)5]2 (M=Ni, 2; Co, 3; Zn, 4). The complexes 2 and 3 were characterized by X-ray diffraction and show octahedral [M(DMF)6]2+ cations with O-coordinated DMF molecules. The [C5(CN)5]- anions show ideal pentagonal symmetry

New Insights into Hexacoordinated Silicon Complexes with 8- Oxyquinolinato Ligands: 1,3-Shift of Si-Bound Hydrocarbyl Substituents and the Influence of Si-Bound Halides on the 8-Oxyquinolinate Coordination Features

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1402-1418 ◽  
Author(s):  
Erik Wächtler ◽  
Alexander Kämpfe ◽  
Katrin Krupinski ◽  
Daniela Gerlach ◽  
Edwin Kroke ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Coordination Chemistry ◽  
Crystal Structures ◽  
Quantum Chemical ◽  
Poor Response ◽  
Molar Ratio ◽  
X Ray Diffraction ◽  
Torsion Angles ◽  
X Ray ◽  
Cp Mas Nmr

Abstract The transsilylation reaction between allyltrichlorosilane and 8-trimethylsiloxyquinoline in the molar ratio 1 : 3 yields the hexacoordinated silicon tris-chelate (oxinate)2Si(adho) (“oxinate” = 8- oxyquinolinate, “adho” = di-anion of 2-allyl-1,2-dihydro-8-oxyquinoline) comprising an SiO3N3 skeleton. The identity of this complex was established by single-crystal X-ray diffraction analysis and 29Si CP=MAS NMR spectroscopy of its chloroform solvate. Benzyltrichlorosilane and dibenzyldichlorosilane, comprising benzyl (Bn) as an “aromatically stabilized allyl moiety” did not undergo such rearrangement. Instead, the complexes (oxinate)2SiBnCl and (oxinate)2SiBn2 were obtained even upon using three molar equivalents of 8-trimethylsiloxyquinoline. We determined the crystal structure of a non-disordered bis-chelate (oxinate)2SiBnCl with Sibound hydrocarbyl and halogen substituents (the previously published (oxinate)2SiMeCl was disordered with alternative Me=Cl site occupancies). (Oxinate)2SiBnCl exhibits surprisingly poor response of the N-Si bonds to the different trans-disposed Si-X (X=Bn, Cl) bonds. For comparison and deeper insights into the coordination chemistry of oxinato silicon complexes with halide substituents, we determined the crystal structures of (oxinate)2SiPhCl·CHCl3, (oxinate)2SiCl2, (oxinate)2SiF2·1.5(CHCl3), and (8-oxyquinaldinate)2SiF2. Furthermore, the crystal structures of BnSiCl3 and Bn2SiCl2 (and its dibromo analog) are reported. The influence of the Si-C-C-C torsion angles of the benzyl group on the 29Si NMR shift of benzylsilanes (which is noticeably upfield with respect to analogous methyl silanes) was analyzed by quantum-chemical calculations.

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