Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II)

S A Carabineiro, L C Silva, P T Gomes, L C J Pereira, L F Veiros, Sofia I Pascu, M T Duarte, S Namorado, R T Henriques

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Abstract

A series of 2-iminopyrrole ligand precursors with increasing bulkiness [HNC4H3C(R)=N-2,6-R'2C6H3] (R = R' = H, 1 a; R = Me, R'= H, 1 b; R = H, R' = Me, 1 c; R = R' = Me, 1 d; R = H, R' = Pr-i, 1 e; R = Me, R' = iPr, 1f) were synthesized and deprotonated with NaH to give the corresponding iminopyrrolyl sodium salts 2a-f. A set of homoleptic bis-ligand Co(II) complexes of the type [CO(k(2) N,/V-NC4H3C(R)=N-2,6-R'2C6H3)21 (R = R'= H, 3a; R = Me, R'= H, 3b; R = H, R' = Me, 3c; R = R' = Me, 3d; R = H, R' = Pr-i, 3e; R = Me, R' = Pr, 3f) was prepared by reaction Of COC12 with the corresponding iminopyrrolyl sodium salts 2a-f. The new complexes were characterized by elemental analysis, magnetic susceptibility measurements, in powder and in solution, UV/vis/NIR, and, in some cases, X-ray crystallography. According to X-ray diffraction and magnetic measurements, the Co complexes 3a-e proved to be tetrahedral, which is the preferred geometry for Co(II) compounds. However, a square planar geometry is observed in the case of 3f, as determined by several characterization techniques. In this case, DFT calculations suggest the square planar geometry is slightly more stable than the tetrahedral one probably due to a combination of steric and electronic reasons.
Original languageEnglish
Pages (from-to)6880-6890
Number of pages11
JournalInorganic Chemistry
Volume46
Issue number17
DOIs
Publication statusPublished - 2007

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Cobalt
cobalt
Geometry
synthesis
Salts
geometry
Sodium
sodium
Ligands
salts
ligands
X ray crystallography
Magnetic variables measurement
Carbon Monoxide
Magnetic susceptibility
Discrete Fourier transforms
Powders
crystallography
magnetic measurement
x rays

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Carabineiro, S. A., Silva, L. C., Gomes, P. T., Pereira, L. C. J., Veiros, L. F., Pascu, S. I., ... Henriques, R. T. (2007). Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II). Inorganic Chemistry, 46(17), 6880-6890. https://doi.org/10.1021/ic062125w

Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II). / Carabineiro, S A; Silva, L C; Gomes, P T; Pereira, L C J; Veiros, L F; Pascu, Sofia I; Duarte, M T; Namorado, S; Henriques, R T.

In: Inorganic Chemistry, Vol. 46, No. 17, 2007, p. 6880-6890.

Research output: Contribution to journalArticle

Carabineiro, SA, Silva, LC, Gomes, PT, Pereira, LCJ, Veiros, LF, Pascu, SI, Duarte, MT, Namorado, S & Henriques, RT 2007, 'Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II)', Inorganic Chemistry, vol. 46, no. 17, pp. 6880-6890. https://doi.org/10.1021/ic062125w
Carabineiro, S A ; Silva, L C ; Gomes, P T ; Pereira, L C J ; Veiros, L F ; Pascu, Sofia I ; Duarte, M T ; Namorado, S ; Henriques, R T. / Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II). In: Inorganic Chemistry. 2007 ; Vol. 46, No. 17. pp. 6880-6890.
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T1 - Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II)

AU - Carabineiro, S A

AU - Silva, L C

AU - Gomes, P T

AU - Pereira, L C J

AU - Veiros, L F

AU - Pascu, Sofia I

AU - Duarte, M T

AU - Namorado, S

AU - Henriques, R T

PY - 2007

Y1 - 2007

N2 - A series of 2-iminopyrrole ligand precursors with increasing bulkiness [HNC4H3C(R)=N-2,6-R'2C6H3] (R = R' = H, 1 a; R = Me, R'= H, 1 b; R = H, R' = Me, 1 c; R = R' = Me, 1 d; R = H, R' = Pr-i, 1 e; R = Me, R' = iPr, 1f) were synthesized and deprotonated with NaH to give the corresponding iminopyrrolyl sodium salts 2a-f. A set of homoleptic bis-ligand Co(II) complexes of the type [CO(k(2) N,/V-NC4H3C(R)=N-2,6-R'2C6H3)21 (R = R'= H, 3a; R = Me, R'= H, 3b; R = H, R' = Me, 3c; R = R' = Me, 3d; R = H, R' = Pr-i, 3e; R = Me, R' = Pr, 3f) was prepared by reaction Of COC12 with the corresponding iminopyrrolyl sodium salts 2a-f. The new complexes were characterized by elemental analysis, magnetic susceptibility measurements, in powder and in solution, UV/vis/NIR, and, in some cases, X-ray crystallography. According to X-ray diffraction and magnetic measurements, the Co complexes 3a-e proved to be tetrahedral, which is the preferred geometry for Co(II) compounds. However, a square planar geometry is observed in the case of 3f, as determined by several characterization techniques. In this case, DFT calculations suggest the square planar geometry is slightly more stable than the tetrahedral one probably due to a combination of steric and electronic reasons.

AB - A series of 2-iminopyrrole ligand precursors with increasing bulkiness [HNC4H3C(R)=N-2,6-R'2C6H3] (R = R' = H, 1 a; R = Me, R'= H, 1 b; R = H, R' = Me, 1 c; R = R' = Me, 1 d; R = H, R' = Pr-i, 1 e; R = Me, R' = iPr, 1f) were synthesized and deprotonated with NaH to give the corresponding iminopyrrolyl sodium salts 2a-f. A set of homoleptic bis-ligand Co(II) complexes of the type [CO(k(2) N,/V-NC4H3C(R)=N-2,6-R'2C6H3)21 (R = R'= H, 3a; R = Me, R'= H, 3b; R = H, R' = Me, 3c; R = R' = Me, 3d; R = H, R' = Pr-i, 3e; R = Me, R' = Pr, 3f) was prepared by reaction Of COC12 with the corresponding iminopyrrolyl sodium salts 2a-f. The new complexes were characterized by elemental analysis, magnetic susceptibility measurements, in powder and in solution, UV/vis/NIR, and, in some cases, X-ray crystallography. According to X-ray diffraction and magnetic measurements, the Co complexes 3a-e proved to be tetrahedral, which is the preferred geometry for Co(II) compounds. However, a square planar geometry is observed in the case of 3f, as determined by several characterization techniques. In this case, DFT calculations suggest the square planar geometry is slightly more stable than the tetrahedral one probably due to a combination of steric and electronic reasons.

UR - http://dx.doi.org/10.1021/ic062125w

U2 - 10.1021/ic062125w

DO - 10.1021/ic062125w

M3 - Article

VL - 46

SP - 6880

EP - 6890

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 17

ER -