FeII Carbonyl Complexes Featuring Small to Bulky PNP Pincer Ligands – Facile Substitution of κ2P,N‐Bound PNP Ligands by Carbon Monoxide

Glatz, Mathias; Holzhacker, Christian; Bichler, Bernhard; Mastalir, Matthias; Stöger, Berthold; Mereiter, Kurt; Weil, Mat­thias; Veiros, Luı́s F.; Mösch‐Zanetti, Nadia C.; Kirchner, Karl

doi:10.1002/ejic.201500646

Cited by 22 publications

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References 71 publications

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“…The structure of the four-coordinate complexes [Fe(κ 2 P , N -PN NH2 - i Pr)Cl 2 ] ( 2a ) shows a distorted tetrahedral coordination environment around the iron center. All bond lengths are consistent with a high-spin electron configuration of Fe 2+ and in reasonable accord with other crystallographically characterized four-coordinate Fe(II) dihalide complexes featuring aminophosphine co-ligands [ 13 – 16 ] (Fig. 2 ).…”

Section: Resultssupporting

confidence: 89%

“…On the other hand, complexation was unsuccessful with the ligand PN NHMe - i Pr ( 1c ) and PN NHEt - t Bu ( 1d ). Instead, the reaction of FeCl 2 with 1c and 1d was accompanied by a phosphine transfer step by a second PN ligand to yield the known complexes [Fe(κ 3 P,N,P -PNP Me - i Pr)Cl 2 ] ( 3a ) and [Fe(κ 3 P,N,P -PNP Et - i Pr)Cl 2 ] ( 3b ) [ 16 ] together with the 2,6-diaminopyridines 4a and 4b as well as intractable iron compounds (Scheme 4 ). Accordingly, the yields of 3a and 3b are less than 50 % being 46 and 48 %, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Accordingly, the yields of 3a and 3b are less than 50 % being 46 and 48 %, respectively. The products were identified by 1 H NMR spectroscopy, after the insoluble inorganic residue was removed by filtration and comparison with the spectra of authentic samples prepared independently [ 16 ].

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Section: Resultsmentioning

confidence: 99%

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High-spin iron(II) complexes with mono-phosphorylated 2,6-diaminopyridine ligands

et al. 2016

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Several new monophosphorylated 2,6-diaminopyridine ligands bearing PiPr2 and PtBu2 units (PNNH2-iPr, PNNH2-tBu, PNNHMe-iPr, and PNNHEt-iPr) are prepared by treatment of the respective 2,6-diaminopyridines with the chlorophosphines PiPr2Cl and PtBu2Cl in the presence of a base. Treatment of anhydrous FeCl2 with 1 equiv of these afforded the tetracoordinated coordinatively unsaturated 14e− complexes [Fe(κ2P,N-PNNH2-iPr)Cl2] and [Fe(κ2P,N-PNNH2-tBu)Cl2], while with PNNHMe-iPr and PNNHEt-iPr a phosphine transfer reaction of a second PN ligand took place to yield the known PNP pincer complexes [Fe(κ3P,N,P-PNPMe-iPr)Cl2] and [Fe(κ3P,N,P-PNPEt-iPr)Cl2]. The four-coordinate complexes [Fe(κ2P,N-PNNH2-iPr)Cl2] and [Fe(κ2P,N-PNNH2-tBu)Cl2] did not react with CO and the formation of iron PNC pincer complexes was not observed. The reason for the reluctance to add CO was investigated in detail by DFT calculations.Graphical abstract

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

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High-spin iron(II) complexes with mono-phosphorylated 2,6-diaminopyridine ligands

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“…They have found use in organometallic chemistry, as their ability to chelate tends to make the metal complexes thermally robust (Selander & Szabó, 2011;Plikhta et al, 2015). In addition, pincer ligands can help tune the properties of the metal center by tuning their steric and electronic properties (Bichler et al, 2014;Glatz et al, 2015). Transition-metal complexes containing pincer ligands have been found to catalyze a range of reactions, including hydrogenation and hydroamination (Schneider et al, 2012;van der Boom & Milstein, 2003).…”

Section: Introductionmentioning

confidence: 99%

Iron pyrrole-based PNP pincer ligand complexes as catalyst precursors

2017

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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 (PNP) has been synthesized. These complexes are possible precursors to new iron catalysts. {2,5-Bis[(diisopropylphosphanyl)methyl]pyrrolido-κP,N,P'}carbonylchlorido(trimethylphosphane-κP)iron(II), [Fe(CHNP)Cl(CHP)(CO)] or [Fe(PNP)Cl(PMe)(CO)], (I), has a slightly distorted octahedral geometry, with the Cl and CO ligands occupying the apical positions. {2,5-Bis[(diisopropylphosphanyl)methyl]pyrrolido-κP,N,P'}chlorido(pyridine-κN)iron(II), [Fe(CHNP)Cl(CHN)] or [Fe(PNP)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-κP,N,P'}dicarbonylchloridoiron(II), [Fe(CHNP)Cl(CO)] or [Fe(PNP)Cl(CO)], (III), is structurally similar to (I), but with the PMe 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.

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“…trans-Fe II (PNP Et )Br 2 (CO)] (2) was prepared in the same manner as trans-Fe II (PNP-Et)Cl 2 (CO)] (Glatz et al, 2015) using FeBr 2 (150 mg, 0.70 mmol) and the ligand PNP-Et (200 mg, 0.70 mmol) as starting materials. Yield: 250 mg (95%).…”

Section: Synthesismentioning

confidence: 99%

Twinning of three Fe-PNP pincer complexes interpreted according to order–disorder (OD) theory

Bichler¹,

Holzhacker²,

Glatz³

et al. 2015

Acta Crystallogr Sect B

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The systematic twinning of three 2,6-diaminopyridine-based Fe-PNP complexes is interpreted using order-disorder (OD) theory. The monoclinic [Fe(0)(PNP(Et)-(i)Pr)(CO)2] [P112(1)/b, Z' = 4] possesses pseudo-orthorhombic metrics and crystallizes as a reflection twin by pseudo-merohedry with the twin plane (100). The structure is made up of layers with idealized p2(1)a(b) symmetry. The a glide planes of adjacent layers do not overlap, leading to OD polytypism. trans-[Fe(II)(PNP-Et)Br2(CO)] [P2(1)/n, Z' = 1] is systematically twinned via twofold rotation about [001]. It is made up of OD layers with idealized p2(1)2(1)(2) symmetry. OD polytypism is caused by the twofold rotation axes of adjacent layers which do not overlap. [Fe(II)(κ(2)P,N-PNP-(i)Pr,TAD)Cl2]·THF [P1, Z^{\prime} = 2] is systematically twinned via a twofold rotation about [010]. It is made up of layers with idealized p121(1) symmetry. OD polytypism is caused by screw rotations relating adjacent layers with an intrinsic translation along a fourth of a primitive lattice vector. In all three structures the twin individuals are a polytype with a maximum degree of order (MDO) and at the twin interface is located a fragment of the second MDO polytype.

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Fe^II Carbonyl Complexes Featuring Small to Bulky PNP Pincer Ligands – Facile Substitution of κ²P,N‐Bound PNP Ligands by Carbon Monoxide

Cited by 22 publications

References 71 publications

High-spin iron(II) complexes with mono-phosphorylated 2,6-diaminopyridine ligands

High-spin iron(II) complexes with mono-phosphorylated 2,6-diaminopyridine ligands

Iron pyrrole-based PNP pincer ligand complexes as catalyst precursors

Twinning of three Fe-PNP pincer complexes interpreted according to order–disorder (OD) theory

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