Iron pyrrole-based PNP pincer ligand complexes as catalyst precursors

2017 ◽  
Vol 73 (7) ◽  
pp. 569-574 ◽  
Author(s):  
Amanda M. Holland ◽  
Allen G. Oliver ◽  
Vlad M. Iluc
Keyword(s):  
Iron Catalysts ◽  
Distorted Octahedral Geometry ◽  
Carbonyl Ligand ◽  
Pyridine Ligand ◽  
Pincer Ligand ◽  
Tridentate Ligands ◽  
Apical Position ◽  
Positional Disorder ◽  
Carbonyl Ligands ◽  
Distorted Octahedral

The structure of a pincer ligand consists of a backbone and two `arms' which typically contain a P or N atom. They are tridentate ligands that coordinate to a metal center in a meridional configuration. A series of three iron complexes containing the pyrrole-based PNP pincer ligand 2,5-bis[(diisopropylphosphanyl)methyl]pyrrolide (PNpyrP) has been synthesized. These complexes are possible precursors to new iron catalysts. {2,5-Bis[(diisopropylphosphanyl)methyl]pyrrolido-κ3 P,N,P′}carbonylchlorido(trimethylphosphane-κP)iron(II), [Fe(C18H34NP2)Cl(C3H9P)(CO)] or [Fe(PNpyrP)Cl(PMe3)(CO)], (I), has a slightly distorted octahedral geometry, with the Cl and CO ligands occupying the apical positions. {2,5-Bis[(diisopropylphosphanyl)methyl]pyrrolido-κ3 P,N,P′}chlorido(pyridine-κN)iron(II), [Fe(C18H34NP2)Cl(C5H5N)] or [Fe(PNpyrP)Cl(py)] (py is pyridine), (II), is a five-coordinate square-pyramidal complex, with the pyridine ligand in the apical position. {2,5-Bis[(diisopropylphosphanyl)methyl]pyrrolido-κ3 P,N,P′}dicarbonylchloridoiron(II), [Fe(C18H34NP2)Cl(CO)2] or [Fe(PNpyrP)Cl(CO)2], (III), is structurally similar to (I), but with the PMe3 ligand replaced by a second carbonyl ligand from the reaction of (II) with CO. The two carbonyl ligands are in a cis configuration, and there is positional disorder of the chloride and trans carbonyl ligands.

scholarly journals fac-[1,2-Bis(pyridin-4-yl)ethane-κN]tricarbonyl(1,10-phenanthroline-κ2N,N′)rhenium(I) hexafluoridophosphate acetonitrile monosolvate

2014 ◽  
Vol 70 (7) ◽  
pp. m278-m279 ◽  
Author(s):  
Silvana Guilardi ◽  
Antonio Otavio Toledo Patrocinio ◽  
Sinval Fernandes de Sousa ◽  
Javier Ellena
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Packing ◽  
Solvent Molecule ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Asymmetric Unit ◽  
Carbonyl Ligands ◽  
Distorted Octahedral ◽  
Phenanthroline Ligand ◽  
Solvent Molecules

The asymmetric unit of the title compound, [Re(C12H8N2)(C12H12N2)(CO)3]PF6.·CH3CN, contains one cation, one hexafluoridophosphate anion and one acetonitrile solvent molecule. The ReIion is coordinated by two N atoms from the 1,10-phenanthroline ligand and one N atom from the 1,2-bis(pyridin-4-yl)ethane ligand [mean Re—N = 2.191 (15) Å] and by three carbonyl ligands [mean Re—C = 1.926 (3) Å] in a distorted octahedral geometry. The electrostatic forces and weak C—H...F(O) hydrogen bonds pack cations and anions into the crystal with voids of 82 Å3, which are filled by solvent molecules. The crystal packing exhibits short intermolecular O...O distance of 2.795 (5) Å between two cations related by inversion.

Preparation and crystal and molecular structure of (η3-octamethylcyclotetraphosphazane-P,P,P)tricarbonylmolybdenum(0), [η3-(CH3PNCH3)4]Mo(CO)3

1982 ◽  
Vol 60 (19) ◽  
pp. 2415-2419 ◽  
Author(s):  
Keith D. Gallicano ◽  
Norman L. Paddock ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Phosphorus Atom ◽  
Mirror Symmetry ◽  
Crystal And Molecular Structure ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Full Matrix ◽  
Carbonyl Ligands ◽  
Distorted Octahedral

The synthesis and physical properties of the phosphazane complex [η3-(CH3PNCH3)4]Mo(CO)3 are reported. Crystals of (η3-octamethylcyclotetraphosphazane-P,P,P)tricarbonylmolybdenum(0) are monoclinic, a = 8.6898(9), b = 16.0987(8), c = 14.1156(17) Å, β = 98.321(6)°, Z = 4, space group Cc. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to R = 0.020 and Rw = 0.024 for 2286 reflections with I ≥ 3σ(I). The molybdenum atom is coordinated to three phosphorus atoms of the (MePNMe)4 ligand and to three carbonyl ligands in a distorted octahedral geometry. The molecule has approximate mirror symmetry in the solid state. Important bond lengths (corrected for libration) are: Mo—P = 2.537(1), 2.467(1), and 2.513(1), Mo—C = 1.971(4), 2.002(4), and 1.978(4), mean P—N = 1.704(8) for coordinated P, 1.735(7) Å for uncoordinated P. The structural evidence indicates that the phosphazane is a weaker donor to Mo(CO)3 than to three sulphur atoms, and that coordination withdraws electron density from the fourth phosphorus atom. The complex is fluxional in solution.

Distorted octahedral environments in tricarbonylrhenium(I) complexes of 5-[2-(2,4,6-trimethylphenyl)diazen-1-yl]quinolin-8-olate and 5,7-bis[2-(2-methylphenyl)diazen-1-yl]quinolin-8-olate

2013 ◽  
Vol 69 (12) ◽  
pp. 1467-1471
Author(s):  
Marietjie Schutte-Smith ◽  
Theunis J. Muller ◽  
Hendrik G. Visser ◽  
Andreas Roodt
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Pyridine Ligand ◽  
Distorted Octahedral Environment ◽  
Carbonyl Ligands ◽  
Hydrogen Bonding Interactions ◽  
Octahedral Environment ◽  
Distorted Octahedral

The ReIcentres of two ReI–tricarbonyl complexes,viz.tricarbonyl(pyridine-κN){5-[2-(2,4,6-trimethylphenyl)diazen-1-yl]quinolin-8-olato-κ2N1,O}rhenium(I), [Re(C23H21N4O)(CO)3], (I), and {5,7-bis[2-(2-methylphenyl)diazen-1-yl]quinolin-8-olato-κ2N1,O}tricarbonyl(pyridine-κN)rhenium(I), [Re(C28H23N6O)(CO)3], (II), are facially surrounded by three carbonyl ligands, a pyridine ligand and either a 5-[2-(2,4,6-trimethylphenyl)diazen-1-yl]quinolin-8-olate [in (I)] or a 5,7-bis[2-(2-methylphenyl)diazen-1-yl]quinolin-8-olate [in (II)] ligand, in a slightly distorted octahedral environment. The crystal structure of (I) is stabilized by two intermolecular C—H...O interactions and that of (II) is stabilized by three intermolecular C—H...O hydrogen-bonding interactions.

scholarly journals Dicarbonyl(η5-cyclopentadienyl)(hexamethylenetetramine-κN1)iron(II) tetrafluoridoborate

2012 ◽  
Vol 68 (8) ◽  
pp. m1077-m1077
Author(s):  
Cyprian M. M'thiruaine ◽  
Holger B. Friedrich ◽  
Bernard Omondi
Keyword(s):  
Title Compound ◽  
Octahedral Geometry ◽  
Distorted Octahedral Geometry ◽  
Asymmetric Unit ◽  
Apical Position ◽  
Bond Lengths ◽  
Coordination Sites ◽  
Cyclopentadienyl Ligand ◽  
Distorted Octahedral

In the structure of the title compound, [Fe(C5H5)(C6H12N4)(CO)2]BF4, the arrangement around the FeIIatom corresponds to that of a three-legged piano stool. The cyclopentadienyl ligand occupies three coordination sites of the apical position in a η5fashion, while two CO ligands and one N atom of the hexamethylenetetramine ligand occupy the remaining coordination sites to complete a distorted octahedral geometry. The asymmetric unit consists of two sets of crystallographically independent cations and anions with the r.m.s. deviations of the overlay of non-H atoms of each pair being 0.081 and 0.120 Å, respectively. The Fe—N bond lengths are 2.0459 (15) and 2.0490 (14) Å, while the Fe—Cp(centroid) distances are 1.7257 (3) and 1.7246 (3) Å. One of the anions displays disorder, with the F atoms having occupancies of 0.58 (4) and 0.42 (4).

scholarly journals Crystal structure of bis{2-hydroxy-N′-[1-(pyrazin-2-yl)ethylidene]benzohydrazidato}cadmium(II)

2021 ◽  
Vol 77 (2) ◽  
pp. 153-157
Author(s):  
Ping Yang ◽  
Xiao-Bao Xie ◽  
Qing-Shan Shi
Keyword(s):  
Crystal Structure ◽  
Complex Molecule ◽  
Octahedral Geometry ◽  
Title Complex ◽  
Distorted Octahedral Geometry ◽  
Tridentate Ligands ◽  
Distorted Octahedral ◽  
Crystallographic Symmetry ◽  
Cu And Zn

In the title complex molecule, [Cd(C13H11N4O2)2], the Cd atom is coordinated in a distorted octahedral geometry by two tridentate ligands synthesized from 2-hydroxybenzohydrazide and 1-(pyrazin-2-yl)ethan-1-one. The molecule has twofold crystallographic symmetry and is isomorphous to its Mn, Co, Ni, Cu and Zn counterparts.

scholarly journals fac-Bromido/chlorido(0.50/0.50)[3-carbamoyl-1-(1,10-phenanthrolin-2-ylmethyl)pyridinium-κ2 N,N′]tricarbonylmanganese(I) 0.49-bromide 0.51-chloride methanol monosolvate

IUCrData ◽  
2018 ◽  
Vol 4 (1) ◽  
Author(s):  
Kosei Wadayama ◽  
Tsugiko Takase ◽  
Dai Oyama
Keyword(s):  
Three Dimensional ◽  
Title Complex ◽  
Asymmetric Unit ◽  
Counter Anion ◽  
Carbonyl Ligand ◽  
Carbonyl Ligands ◽  
Octahedral Environment ◽  
Dimensional Network ◽  
Distorted Octahedral ◽  
Chloride Ligand

The title complex, [MnBr0.50Cl0.50(C19H15N4O)(CO)3]Br0.49Cl0.51·CH3OH, exhibits substitutional disorder of the halogen ligand in the asymmetric unit, with almost the same occupancies for Br and Cl. The MnI atom is coordinated in a distorted octahedral environment by three carbonyl C atoms, the disordered X − ligand (X = Br or Cl) and two N atoms from the 1,10-phenanthroline ligand bearing a nicotinamide pendant moiety. The cation displays a fac configuration of the carbonyl ligands. There is another disorder between the chloride ligand and its trans-situated carbonyl ligand, and between Cl− and Br− at the position of the counter-anion. In the crystal, intermolecular C—H...X, N—H...X, O—H...X (X = Br or Cl) and C—H...O hydrogen bonds lead to the formation of a three-dimensional network.

scholarly journals Crystal structure of bromido-fac-tricarbonyl[5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ2N2,N3]rhenium(I) methanol monosolvate

2017 ◽  
Vol 73 (4) ◽  
pp. 484-487
Author(s):  
Marharyta I. Kharlova ◽  
Kseniia O. Piletska ◽  
Kostiantyn V. Domasevitch ◽  
Alexander V. Shtemenko
Keyword(s):  
Hydrogen Bonds ◽  
Double Layers ◽  
Carbonyl Ligand ◽  
Complex Molecules ◽  
Carbonyl Ligands ◽  
Distorted Octahedral Coordination ◽  
Distorted Octahedral ◽  
Triazole Ligand ◽  
Solvent Molecules ◽  
Centrosymmetric Dimers

In the title compound, [ReBr(C16H16N4O3)(CO)3]·CH3OH, the ReIatom adopts a distorted octahedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in axial positions. Conventional hydrogen bonds including the methanol solvent molecules assemble the complex molecules through mutual N—H...O—H...Br links [N...O = 2.703 (3) Å and O...Br = 3.255 (2) Å] into centrosymmetric dimers, whereas weaker C—H...O and C—H...Br hydrogen bonds [C...O = 3.215 (3)–3.390 (4) Å and C...Br = 3.927 (3) Å] connect the dimers into double layers parallel to the (111) plane.

Iminopyridine ligand complexes of group 14 dihalides and ditriflates – neutral chelates and ion pair formation

2017 ◽  
Vol 72 (11) ◽  
pp. 883-894
Author(s):  
Johanna Flock ◽  
Beate Steller ◽  
Petra Unger ◽  
Birgit Gerke ◽  
Rainer Pöttgen ◽  
...  
Keyword(s):  
Solid State ◽  
Ion Pairs ◽  
Distorted Octahedral Geometry ◽  
X Ray Diffraction ◽  
Group 14 ◽  
Pyridine Ligand ◽  
Chloride Complexes ◽  
Tin Chloride ◽  
Distorted Octahedral ◽  
Neutral Compounds

AbstractReaction of the chelating imino-pyridine ligand SIMPY, (SIMPY=2-(DippN=CH)-C5H4N), Dipp=2,6-iPr2-C6H3, with germanium(II) and tin(II) halides provides the respective neutral complexes [SIMPY·EX2] (EX2: E=Ge, X=Cl, Br; E=Sn, X=Cl, Br, I). The method is readily extendable to give the tin(II) triflate complex [SIMPY·Sn(OTf)2] (OTf, triflate=CF3SO3−). In the solid state, the neutral compounds [SIMPY·EX2] exist as monomers, in which the four-coordinate tetrel atoms feature a slightly distorted disphenoidal geometry around germanium and tin. Reaction of the tridentate imino-pyridine ligand DIMPY, (DIMPY=2,6-(DippN=CH)2-C5H3N) with Sn(OTf)2 provided access to a neutral tin(II) complex. Similar to the previously reported reactions leading to the germanium and tin chloride complexes [DIMPY·SnCl]+[SnCl3]−, and [Me2DIMPY·EX]+[EX3]− (Me2DIMPY=2,6-(DippN=C(Me))2-C5H3N, E=Ge, Sn; X=Cl), the reactions of DIMPY with GeX2·dioxane (X=Cl, Br) and SnX2 (X=Br, I) yielded Ge(II) and Sn(II) based ion pairs [DIMPY·EX]+[EX3]− (E=Ge, X=Cl, Br; E=Sn, X=Br, I) as a consequence of spontaneous dissociation of the group 14 dihalides. The tetrel atoms in the cationic parts in [DIMPY·EX]+[EX3]− are four-coordinate as one halide substituent is replaced by the coordination of a second imino donor group from the ligand. The anionic fragments adopt a pyramidally, tri-coordinate geometry. In contrast, the DIMPY tin(II) ditriflate complex crystallizes with two independent, neutral molecules per asymmetric unit, in which one of the tin centers is five- coordinate by interaction with three donor sites of the chelating bis(imino)pyridine ligand and two additional contacts towards the oxygen atoms of the triflate counter-anions. In the second crystallographically independent complex the tin atom is six-coordinate with a slightly distorted octahedral geometry via interaction with THF as an additional donor molecule. All compounds reported were studied by means of multinuclear NMR spectroscopy. In addition, the solid state structures of the complexes [SIMPY·EX2] (EX2: E=Ge, X=Cl, Br; E=Sn, X=Cl, Br, I), the ion pairs [DIMPY·EX]+[EX3]− (E=Ge, X=Cl; E=Sn, X=Br) and the tin(II) ditriflate [DIMPY·Sn(OTf)2] were authenticated by means of single-crystal X-ray diffraction analyses. Moreover, [DIMPY·Sn(OTf)2] was investigated by 119Sn Mössbauer spectroscopy.

scholarly journals Molecular structure of fac-[Mo(CO)3(DMSO)3]

2021 ◽  
Vol 77 (5) ◽  
pp. 583-587
Author(s):  
Benedict J. Elvers ◽  
Christian Fischer ◽  
Carola Schulzke
Keyword(s):  
Dimethyl Sulfoxide ◽  
Three Dimensional ◽  
Carbonyl Carbon ◽  
Carbonyl Ligand ◽  
Complex Molecules ◽  
Triclinic Space Group ◽  
Carbonyl Ligands ◽  
Distorted Octahedral ◽  
Ft Ir ◽  
Ir Bands

The title compound, tricarbonyltris(dimethyl sulfoxide)molybdenum, [Mo(C2H6OS)3(CO)3] or fac-[Mo(CO)3(DMSO)3], crystallizes in the triclinic space group P\overline{1} with two molecules in the unit cell. The geometry around the central molybdenum is slightly distorted octahedral and the facial isomer is found exclusively. The packing within the crystal is stabilized by three-dimensional non-classical intermolecular hydrogen-bonding contacts between individual methyl substituents of dimethyl sulfoxide and the oxygen atoms of either another dimethyl sulfoxide or a carbonyl ligand on adjacent complex molecules. The observed bond lengths in the carbonyl ligands and between carbonyl carbon atoms and molybdenum are correlated to the observed FT–IR bands for the carbonyl stretches and compared to respective metrical parameters of related complexes.

scholarly journals Crystal structures of the [IrIII{C(C4H6O2)(dppm)-κ3 P,C,O}(dppm)H](CF3O3S)2 and [IrIII{C(C4H6O2)(dppm)-κ2 P,C}(CO)(dppm)H](CF3O3S)2 phosphorus ylide complexes, generated by a Wittig-type carbon–carbon coupling reaction of a carbodiphosphorane PCP ligand system

2018 ◽  
Vol 74 (11) ◽  
pp. 1643-1647 ◽  
Author(s):  
Inge Schlapp-Hackl ◽  
Bettina Pauer ◽  
Christoph Falschlunger ◽  
Walter Schuh ◽  
Holger Kopacka ◽  
...  
Keyword(s):  
Chelate Ring ◽  
Coupling Reaction ◽  
Carbonyl Ligand ◽  
Pincer Ligand ◽  
Positional Disorder ◽  
Phosphorus Ylide ◽  
Ligand System ◽  
Coupling Reagent ◽  
Pcp Pincer ◽  
Ylide Complexes

The reaction of [IrIII{C(dppm)2-κ3 P,C,P′}ClH(NH3C2)]Cl with ethyl diazoacetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodiphosphorane system to a phosphorus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The phosphorus electron-donor atoms and the ylide carbon atom of the resulting [IrIII{C(C4H6O2)(dppm)-κ3 P,C,O}(dppm)H](CF3O3S)2 complex, also termed as [bis(diphenylphosphanyl)methane]({[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methanylidene-κ3 P,C,O)hydridoiridium(III) bis(trifluoromethanesulfonate), are in plane and the hydrido ligand and the carbonyl O atom are located trans to each other, perpendicular to the meridional plane. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand, thereby creating [bis(diphenylphosphanyl)methane]carbonyl({[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methanylidene-κ2 P,C}hydridoiridium(III) bis(trifluoromethanesulfonate)–dichloromethane–ethyl acetate (6/2/3) or, more simply, [IrIII{C(C4H6O2)(dppm)-κ2 P,C}(CO)(dppm)H](CF3O3S)2·0.33CH2Cl2·0.5C4H8O2. One trifluoromethanesulfonate counter-ion of 3 shows positional disorder in a 2:1 ratio. Complex 4 shows pseudo-merohedral twinning (matrix: \overline{1} 0 0 0 \overline{1} 0 1 0 1). The dichloromethane solvent is disordered over two orientations with occupation factors of 0.5 and 0.166.

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