High-spin five-coordinate [ML5]2+ and [ML4(ClO4)]+ complexes with trimethylphosphine oxide and trimethylarsine oxide

Brodie, Andrew M.; Hunter, S. H.; Rodley, G. A.; Wilkins, C. J.

doi:10.1016/s0020-1693(00)87025-5

Cited by 83 publications

(6 citation statements)

References 17 publications

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“…For the Fe(II) ion in TMU, we can see absorptions at lower than 5000 and at 8600 (e = 6 M-1 cm-1) cm-1 due to the d-d transitions and at higher than 23 000 cm-1 with a gradual increase in intensity owing to the charge transfer (Figure 4b). The absorption pattern is similar to that of [Fe(m3po)4(OC103)j(C104) (m3po = trimethylphosphine oxide), 39 [Fe(m3ao)4(OC103)](C104) (m3ao = trimethylarsine oxide),39 and [Fe(n2ppo)4(OC103)] -(C104), 49 which have symmetry with the FeOs chromophore. Thus, it is likely that the solvation structure of Fe(II) ion in TMU is five-coordinated square pyramidal (C^, = ~10 000 cm-1).…”

Section: Resultsmentioning

confidence: 61%

Solvation Structures of Manganese(II), Iron(II), Cobalt(II), Nickel(II), Copper(II), Zinc(II), Cadmium(II), and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy. Variation of Coordination Number

Inada¹,

Sugimoto²,

Ozutsumi³

et al. 1994

Inorg. Chem.

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The structures of solvated complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and In(III) ions in 1,1,3,3-tetramethylurea (TMU) have been determined by means of EXAFS (extended X-ray absorption fine structure) and electronic spectroscopy. The solvation structures in TMU are square pyramidal for the Mn(II) and Ni(II) ions, distorted tetrahedral for the Co(II) and Cu(II) ions, tetrahedral for the Zn(II) ion, and octahedral for the Cd(II) and In(III) ions, while in water all these metal ions are six-coordinated octahedrons. The solvation structure of Fe(II) ion is square pyramidal or trigonal bipyramidal. In the bulky TMU solvent, the coordination number should be reduced for relaxation of the sterically repulsive interaction around the solvated metal ions. The metal-oxygen (M-O) bond lengths of solvated metal ions in TMU are

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Section: Resultsmentioning

confidence: 61%

Solvation Structures of Manganese(II), Iron(II), Cobalt(II), Nickel(II), Copper(II), Zinc(II), Cadmium(II), and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy. Variation of Coordination Number

Inada¹,

Sugimoto²,

Ozutsumi³

et al. 1994

Inorg. Chem.

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“…Hydrogens bonded to carbon atoms are omitted for clarity. Figure 4: The X-ray crystal structure of [ZnCl2(Pip3PSe)]2 (6). Hydrogens bonded to carbon atoms are omitted for clarity.…”

Section: Figurementioning

confidence: 99%

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mentioning

confidence: 99%

Synthesis, characterization, and structural properties of mercury(II), cadmium(II) and zinc(II) tripiperidinophosphine chalcogenide complexes

et al. 2019

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Reaction of metal chlorides (MCl2) with tripiperidinophosphine chalcogenides (Pip3PE) produces new dimer species (1)(2)(3)(4)(5)(6) of the formula [MCl2(Pip3PE)]2 (Pip = piperidinyl; E = S or Se; M = Hg, Cd or Zn). These coordination complexes were characterized by elemental analysis, IR, multinuclear ( 31 P, 113 Cd and 199 Hg) NMR spectroscopy and single crystal X-ray analysis. Compounds 1-6 exist as centrosymmetric homobimetallic dimers, [M(µ-Cl)Cl(Pip3PE)]2. Each dimer incorporates two µ2-chloro atoms and two terminal M-Cl bonds. The E atom of Pip3PE forms terminal M-E bonds {S; 2.305(11); Se: 2.412(6)-2.589(15) Å} and thus the geometry about each metal centre is distorted tetrahedral and the range of tetrahedral bond angles is 102.83(3) to 113.32(3) o . The P=Se bond lengths of 2.183(9)-2.205(2) Å in the selenide complexes are slightly elongated compared to those in the free ligands [2.1090(4) Å]. The results are discussed and compared with those obtained for related analogues.

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“…A further illustration of the ambiguity in the simple vibrational method is found in complexes of M3+ and me3PO or me3AsO, ML4(C104) + (23). Although X-ray powder patterns indicate the similarity of these complexes to MLg2+ and thus imply coordinated perchlorate, the infrared spectra do not indicate the expected splitting.…”

Section: Perchlorate Ion and Tetrafluoroborate Ionmentioning

confidence: 99%

The myth of the non-coordinating anion

Rosenthal¹

1973

J. Chem. Educ.

504

221

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High-spin five-coordinate [ML5]2+ and [ML4(ClO4)]+ complexes with trimethylphosphine oxide and trimethylarsine oxide

Cited by 83 publications

References 17 publications

Solvation Structures of Manganese(II), Iron(II), Cobalt(II), Nickel(II), Copper(II), Zinc(II), Cadmium(II), and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy. Variation of Coordination Number

Solvation Structures of Manganese(II), Iron(II), Cobalt(II), Nickel(II), Copper(II), Zinc(II), Cadmium(II), and Indium(III) Ions in 1,1,3,3-Tetramethylurea As Studied by EXAFS and Electronic Spectroscopy. Variation of Coordination Number

Synthesis, characterization, and structural properties of mercury(II), cadmium(II) and zinc(II) tripiperidinophosphine chalcogenide complexes

The myth of the non-coordinating anion

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