Spin Density Distribution in Iron(II) and Cobalt(II) Alkyl Complexes Containing 1,3-Bis(2-pyridylimino)isoindolate Ligands

Sauer, Désirée C.; Kruck, Matthias; Wadepohl, Hubert; Enders, Markus; Gade, Lutz H.

doi:10.1021/om301198b

Cited by 20 publications

(18 citation statements)

References 78 publications

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“… 6 − 10 It has to be noted that several related cobalt complexes containing anionic pincer-type PNP, PSiP, NCN, and NNN frameworks are described. 11 − 19 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues

Murugesan¹,

Stöger²,

Carvalho³

et al. 2014

Organometallics

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Anhydrous CoCl2 or [NiCl2(DME)] reacts with the ligand PCPMe-iPr (1) in the presence of nBuLi to afford the 15e and 16e square planar complexes [Co(PCPMe-iPr)Cl] (2) and [Ni(PCPMe-iPr)Cl] (3), respectively. Complex 2 is a paramagnetic d7 low-spin complex, which is a useful precursor for a series of Co(I), Co(II), and Co(III) PCP complexes. Complex 2 reacts readily with CO and pyridine to afford the five-coordinate square-pyramidal 17e complexes [Co(PCPMe-iPr)(CO)Cl] (4) and [Co(PCPMe-iPr)(py)Cl] (5), respectively, while in the presence of Ag+ and CO the cationic complex [Co(PCPMe-iPr)(CO)2]+ (6) is afforded. The effective magnetic moments μeff of all Co(II) complexes were derived from the temperature dependence of the inverse molar magnetic susceptibility by SQUID measurements and are in the range 1.9 to 2.4 μB. This is consistent with a d7 low-spin configuration with some degree of spin–orbit coupling. Oxidation of 2 with CuCl2 affords the paramagnetic Co(III) PCP complex [Co(PCPMe-iPr)Cl2] (7), while the synthesis of the diamagnetic Co(I) complex [Co(PCPMe-iPr)(CO)2] (8) was achieved by stirring 2 in toluene with KC8 in the presence of CO. Finally, the cationic 16e Ni(II) PCP complex [Ni(PCPMe-iPr)(CO)]+ (10) was obtained by reacting complex 3 with 1 equiv of AgSbF6 in the presence of CO. The reactivity of CO addition to Co(I), Co(II), and Ni(II) PCP square planar complexes of the type [M(PCPMe-iPr)(CO)]n (n = +1, 0) was investigated by DFT calculations, showing that formation of the Co species, 6 and 8, is thermodynamically favorable, while Ni(II) maintains the 16e configuration since CO addition is unfavorable in this case. X-ray structures of most complexes are provided and discussed. A structural feature of interest is that the apical CO ligand in 4 deviates significantly from linearity, with a Co–C–O angle of 170.0(1)°. The DFT-calculated value is 172°, clearly showing that this is not a packing but an electronic effect.

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“… 6 − 10 It has to be noted that several related cobalt complexes containing anionic pincer-type PNP, PSiP, NCN, and NNN frameworks are described. 11 − 19 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues

Murugesan¹,

Stöger²,

Carvalho³

et al. 2014

Organometallics

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“…Conversely, the synthesis of complexes where coordination numbers of six are favorable can sometimes be more challenging and may require bulky ligands and/or an excess of the metal salt to be used in order to avoid formation of the homoleptic complex of the tridentate donor, ML 2 [30,34] (e.g., see [40][41][42]). This was observed, for example, in the synthesis of BPI complexes in which ligands are substituted adjacent to the pyridine nitrogen atom [43][44][45]. This results in steric shielding of the metal center in the complex, precluding the addition of a second ligand, and therefore, the heteroleptic complexes [(BPI)M(X)(S) n )] could be obtained (Scheme 7) [43].…”

Section: Ligand Designmentioning

confidence: 96%

New Chemistry with Anionic NNN Pincer Ligands

Melen

Gade

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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The use of tridentate anionic pincer ligands in organometallic chemistry has gained considerable importance, particularly in the field of homogenous catalysis. This chapter focuses on the recent developments of anionic tridentate NNN pincer ligands from their synthesis to coordination chemistry and their applications in forming stable transition metal complexes for applications in catalytic transformations.

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“…Moreover, partial orientational ordering of the magnetically anisotropic iron(II) complexes in high magnetic fields led to the observation of very large residual dipolar 13 C– 1 H coupling, which not only allowed a detailed determination of the solution structure, but also the identification of both the axial and rhombic components of the magnetic susceptibility tensors 14. Fe II – and Co II –BPI complexes containing alkyl ligands have also been prepared and characterised in the solid state and in solution 15…”

Section: Versatile Transition‐metal Coordination Modesmentioning

confidence: 99%

Chromophores, Fluorophores and Robust Ancillary Ligands for Molecular Catalysts: 1,3‐Bis(2‐pyridylimino)isoindolines

et al. 2014

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Since the first report in the early 1950s, 1,3‐bis(2‐pyridylimino)isoindolines (BPIs) have found widespread applications in organic, inorganic and materials chemistry. This microreview focuses on recent progress towards chiral BPI derivatives as ligands for enantioselective catalysis as well as developments in the use of BPI complexes in materials science, focusing on luminescent and birefringent materials.

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Spin Density Distribution in Iron(II) and Cobalt(II) Alkyl Complexes Containing 1,3-Bis(2-pyridylimino)isoindolate Ligands

Cited by 20 publications

References 78 publications

Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues

Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues

New Chemistry with Anionic NNN Pincer Ligands

Chromophores, Fluorophores and Robust Ancillary Ligands for Molecular Catalysts: 1,3‐Bis(2‐pyridylimino)isoindolines

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