Molecular structures and solid-solid phase transitions of trinuclear CpCo[P(O)(OR)2]3 2M complexes

Dubler, E.; Linowsky, Lothar; Kläui, Wolfgang

doi:10.1007/bf00619066

Cited by 26 publications

(9 citation statements)

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“…2. The structure shows essentially the same feature as those of copper and cobalt complexes (Dubler et al, 1979). The two cyclopentadienyl rings are parallel to each other representing a sandwich type of complex.…”

Section: Description Of the Structure And Discussionmentioning

confidence: 72%

“…Kläui and coworkers prepared a series of trinuclear complexes of the general formula {c/>Co[P(0)(OR) 2 ]3} 2 M, where M = Mg, Ca, Sr, Ba, Pb, Mn, Co, Ni, Cr, Zn, Cd or Hg (Dubler et al, 1979). The structure of To whom correspondence should be addressed: Professor B. Kamenar, Laboratory of General and Inorganic Chemistry, Faculty of Science, Ulica soc.…”

Section: Introductionmentioning

confidence: 98%

See 1 more Smart Citation

Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Kamenar¹,

Hergold-Brundić²,

Bravo³

1988

Zeitschrift Für Kristallographie - Crystalline Materials

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The crystal and molecular structure of the title trinuclear complex has been determined from three-dimensional diffractometer data by Patterson and Fourier methods. Crystals are triclinic, space group Pi, a = 12.042(4), b = 20.359(11), c= 12.694(6) Â, α =101.51(4), 0 = 118.51(2), y = 92.20(4)° and isomorphous with the analogous copper complex. Data were refined by the least-squares procedure to R = 0.056 for 3732 independent reflections. There are two independent complex molecules in the unit cell with mercury atoms in two different centres of symmetry. The structure consists of linear Co...Hg...Co systems bridged by diethylphosphonate groups. Co...Hg separations amount to 4.078 Â in one and 4.065 Â in the other molecule. The Co atoms are surrounded by cyclopentadienyl rings and three Ρ atoms from diethylphosphonate groups. The mean values of the Co-C distances are 2.09 and 2.07 À, those of the Co -Ρ bond lengths 2.174 and 2.185 Â. The Hg atoms surrounded by six phosphonate-oxygens have fairly regular octahedral coordination with small (4+2) distortion. The mean values of the Hg-O bond lengths are 2.292 and 2.270 Â. The Ρ atom positions are disordered.

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Section: Description Of the Structure And Discussionmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 98%

Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Kamenar¹,

Hergold-Brundić²,

Bravo³

1988

Zeitschrift Für Kristallographie - Crystalline Materials

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“…Chart 2 Bond lengths/Å of the core structures of complexes 2b and 2c. κ 1 : κ 1 2 .0 9 7 (8 ) 2.1 62 (8) 2.009(8) 2.0 63 (7) 2.150(8) 2 .0 9 3 ( 9 ) 2.060(9) 1.29(1) (bond lengths in Å) 1.23(1) 1.23(1) 1.33(1) 1.20(1) 1.25(2) 1.23(2) 1.27(1) 1 κ 1 : κ 1 2 .1 0 4 (4 ) 2.1 58 (4) 1.992(5) 2.0 79 (4) 2.125(5) 2 .0 8 1 ( 5 ) 2.036(5) 1.243(6) 1.285(6) 1.219(8) 1.318( 7) 1.198(7) 1.297 (9) 1.225 (8) 1.242 (9) 1.281(7) 2c complexes but again dinuclear complexes (Scheme 1). Reaction of LiL OEt (in MeOH) and LiL OiPr (in THF) with Ni(NO 3 ) 2 gave the dinuclear complexes 2a (L = MeOH) and 2c (L = THF), respectively, which were characterized by X-ray crystallography (Fig.…”

Section: Reaction Of Nalmentioning

confidence: 99%

Synthesis and crystal structures of mononuclear half-sandwich complexes of Ni and Co containing Kläui’s tripodal ligand, [M{κ3-(η5-C5H5)Co[P(O)(OCH3)2]3}(κ2-NO3)(L)] (M = Ni or Co)

Akita¹,

Ma²,

Hikichi³

et al. 1999

J. Chem. Soc., Dalton Trans.

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“…In addition, EPR experiments on pure and on copper-doped Zn(mtz) 6 (BF 4 ) 2 have been carried out, and a preliminary communication dealing with part of the EPR work has appeared previously . There are several other literature examples of copper(II) complexes containing two crystallographically inequivalent Jahn−Teller-active centers, namely, Cu(hb(pz) 3 ) 2 [hb(pz) 3 = hydrotris(pyrazolyl)borate], Cu(en) 3 Cl 2 · 3 / 4 en (en = 1,2-ethylenediamine), Cu(Et-cPO) 2 [Et−cPO = cyclopentadienyl)tris(diethyl phosphito- P )cobaltate ion], [Cu(H 2 O) 6 ](bs) 2 (bs = benzenesulfonate), and very recently Cu(ttcn) 2 (BF 4 ) 2 · 2MeCN (ttcn = trithiacyclononane). However, this appears to be the first example where an attempt has been made to understand the difference between the two centers in terms of the local-site strains arising from the crystal packing.…”

Section: Introductionmentioning

confidence: 99%

Disordered CuN₆ Jahn−Teller Centers in Hexakis(1-methyltetrazole)copper(II) Tetrafluoroborate: A Temperature-Dependent X-ray Diffraction and EPR Study

et al. 1996

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The influence of the molecular crystalline arrangement upon the state of a Jahn-Teller-active center has been investigated in crystals of the complex Cu(mtz)(6)(BF(4))(2), where mtz = 1-methyltetrazole. Crystal structures at 293, 123, and 93 K were determined by X-ray diffraction for the copper complex and at 293 and 100 K also for the analogous zinc complex, Zn(mtz)(6)(BF(4))(2). The respective lattice parameters for the copper complex at 293, 123, and 93 K are as follows: a = 18.137(4), 17.597(4), 17.575(4) Å; b = 10.247(4), 10.131(4), 10.133(4); c = 18.446(5), 18.531(4), 18.535(4) Å; beta = 112.62(2), 113.55(2), 113.61(2) degrees. Those for the zinc complexes at 293 and 100 K, respectively, are as follows: a = 18.153(2), 17.663(2) Å; b = 10.289(1), 10.159(2) Å; c = 18.506(3), 18.578(3) Å; beta = 113.21(1), 114.15(2) degrees. The crystal system is monoclinic, space group P2(1)/n (Z = 4), for all crystals with two crystallographically inequivalent pairs of centrosymmetric molecules, M(mtz)(6)(BF(4))(2), in the unit cell. The two inequivalent Cu(mtz)(6)(2+) complexes, Cu(A) and Cu(B), both exhibit Jahn-Teller distortions, but in different ways, the Cu-N distances for the unit on site A being 2.015(4), 2.031(5), and 2.384(5) Å at 93 K, while those for the unit on site B are 2.053(5), 2.126(5), and 2.204(5) Å. However, the Jahn-Teller radii of the two complexes, as calculated from the metal-ligand distances and the U tensors of the two CuN(6) units, were both found to be 0.41(3) Å. EPR experiments at room temperature on polycrystalline samples of the pure copper compound and of the copper-doped zinc compound confirm the presence of two different Jahn-Teller centers; both complexes are rapidly pulsating, but the CuN(6) units on site A are confined predominantly to one potential well of the warped Mexican hat potential, whereas the CuN(6) units on site B have density in all three wells. At 78 K, however, the spectrum of the polycrystalline material is consistent with a single site having an axial g tensor with maximum anisotropy (g( parallel) = 2.300(5), g( perpendicular) = 2.068(5)). While the low-temperature X-ray results also indicate a structure in which the Cu(A) center is exclusively populated in one potential well, the U tensor and potential well population data for the Cu(B) centers indicate that at 93 K a nonpulsating averaged structure based on tetragonally elongated CuN(6) units is being observed. The more pronounced preference for the CuN(6) octahedron on site A to show elongation in one specific direction, in contrast to that on the B site, appears to be due to the differing impacts of the local-site strains at the two distinct centers of symmetry, and a simple model for evaluating a crystal "packing" strain from the bond length data for the isomorphous zinc complex is described.

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Molecular structures and solid-solid phase transitions of trinuclear CpCo[P(O)(OR)2]3 2M complexes

Cited by 26 publications

References 10 publications

Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Synthesis and crystal structures of mononuclear half-sandwich complexes of Ni and Co containing Kläui’s tripodal ligand, [M{κ3-(η5-C5H5)Co[P(O)(OCH3)2]3}(κ2-NO3)(L)] (M = Ni or Co)

Disordered CuN₆ Jahn−Teller Centers in Hexakis(1-methyltetrazole)copper(II) Tetrafluoroborate: A Temperature-Dependent X-ray Diffraction and EPR Study

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Molecular structures and solid-solid phase transitions of trinuclear CpCo[P(O)(OR)2]3 2M complexes

Cited by 26 publications

References 10 publications

Molecular and crystal structure of {cpCo[P(OXOC2H5)2]3}2Hg

Molecular and crystal structure of {cpCo[P(OXOC2H5)2]3}2Hg

Synthesis and crystal structures of mononuclear half-sandwich complexes of Ni and Co containing Kläui’s tripodal ligand, [M{κ3-(η5-C5H5)Co[P(O)(OCH3)2]3}(κ2-NO3)(L)] (M = Ni or Co)

Disordered CuN6 Jahn−Teller Centers in Hexakis(1-methyltetrazole)copper(II) Tetrafluoroborate: A Temperature-Dependent X-ray Diffraction and EPR Study

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Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Molecular and crystal structure of {cpCo[P(OXOC₂H₅)₂]₃}₂Hg

Disordered CuN₆ Jahn−Teller Centers in Hexakis(1-methyltetrazole)copper(II) Tetrafluoroborate: A Temperature-Dependent X-ray Diffraction and EPR Study