Sterically encumbered pyrrolyl ligands and their incorporation into the cycloheptatrienyl zirconium coordination sphere

Kreye, Markus; Glöckner, Andreas; Daniliuc, Constantin G.; Freytag, Mat­thias; Jones, Peter G.; Tamm, Matthias; Walter, Marc D.

doi:10.1039/c2dt32433d

Cited by 17 publications

(18 citation statements)

References 95 publications

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“…The NPNPN moiety is η 5 ‐coordinated, with the potassium atom positioned underneath the five‐membered pyrrolyl‐ring; the K1−N1 distance is 3.0234(12) Å and the K−C distances vary in the range 3.0031(14)–3.3160(14) Å. This structural motif is similar to that found for the related potassium pyrrolyl complex [(3,4‐Me 2 ‐2,5‐tBu 2 ‐C4 N)K(18‐crown‐6)] [20] …”

Section: Resultssupporting

confidence: 74%

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Pyrrole‐based pincer ligands containing iminophosphorane moieties and their coordination chemistry with group 1 metals and magnesium

Ehrlich

Freytag

Raeder

et al. 2021

Zeitschrift anorg allge chemie

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The Staudinger reaction of 2,5‐bis((di‐tert‐butylphosphaneyl)methyl)‐1H‐pyrrole (tBuPNP)H; tBuPNP=C4H2N‐2,5‐CH2PtBu2) with 2 equiv. of Me3SiN3 cleanly furnishes 1,1′‐((1H‐pyrrole‐2,5‐diyl)bis(methylene))bis(1,1‐di‐tert‐butyl‐N‐(trimethylsilyl)‐λ5‐phosphanimine) (1; (NPNPN)H, NPNPN=C4H2N‐2,5‐CH2PtBu2NSiMe3) in excellent yield. Pyrrole 1 is easily deprotonated by alkali metal amides, [MN(SiMe3)2] (M=Li, Na, K, Cs) to yield the corresponding alkali metal pyrrolides, 1‐M. Compound 1‐Li is features a κ‐N,N,N coordination whereby both iminophosphorane side‐arms are coordinated to the lithium cation (with additional short Li⋅⋅⋅H contacts, whereas the heavier congeners form dimeric structures. This results in κ‐N,N coordination within one [(NPNPN)M] (M=Na, Cs) unit, and the dimeric structure is then completed by additional η5‐coordination of the pyrrolyl ligand to the neighbouring alkali metal. Furthermore, heteroleptic magnesium alkyl complexes, 1‐MgR, are isolated from the reaction of [MgR2] (R= CH2SiMe3, CH2CMe3, CH2CMe2Ph) with (PNP*)H (1 equiv).

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Section: Resultssupporting

confidence: 74%

“…This structural motif is similar to that found for the related potassium pyrrolyl complex [(3,4-Me 2 -2,5-tBu 2 -C4 N)K (18-crown-6)]. [20]…”

Section: Synthesis Of Group 1 Complexessupporting

confidence: 82%

Pyrrole‐based pincer ligands containing iminophosphorane moieties and their coordination chemistry with group 1 metals and magnesium

Ehrlich

Freytag

Raeder

et al. 2021

Zeitschrift anorg allge chemie

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“…The H1⋯O distance is somewhat longer than the 1.99(3) Å in 1-H•THF. 20 The ring C-C bond lengths show the typical short-long-short pattern as previously observed for 1-H 20 and Pyr tBu2Me 2 H. 37 The electron delocalization within the pyrrole system can be deduced from the individual CC bond distances, which are intermediate between the distances of isolated single (d 0 (C-C) = 1.54 Å) 40 and double (d 0 (CvC) = 1.34 Å) 40 bonds. The extent of delocalization within the heterocyclic ring can be described by the parameter τ, the normalized quotient of the single and double bond length (eqn (1)) [41][42][43]…”

Section: Introductionsupporting

confidence: 71%

“…34 Whereas tetramethylpyrrole reacts with PCl 3 exclusively at the N-atom, 35 phosphorylation of 2,5-dimethylpyrrole occurs exclusively at the C3-position. 34 In our previous contributions we reported on the synthesis of several sterically encumbered pyrrolyls and the subsequent synthesis of several azatrozircenes [(η 7 -C 7 H 7 )Zr(η 5 -Pyr′)] 36,37 and more recently of diazaferrocenes. 38 Herein, we detail the synthesis of phosphinesubstituted pyrroles (Fig.…”

Section: Introductionmentioning

confidence: 99%

Phosphine-substituted sterically encumbered pyrrolyl ligands – synthesis and reactivity studies

et al. 2013

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The sterically encumbered pyrrolyl KPyr(tBu2) (1-K, Pyr(tBu2) = 2,5-(Me3C)2C4H2N) reacts with PCl3, (iPr)2PCl and Ph2PCl exclusively at the C3-position to yield a series of phosphine-substituted pyrroles HPyr(tBu2R) (R = PCl2 (2-H), (iPr)2P (4-H) and Ph2P (5-H)). Pyrrole 2-H can further be functionalized with MeLi (3 equiv.) to yield LiPyr(tBu2PMe2) (3-Li). The coordination chemistry of these phosphine-substituted pyrroles was explored and the resulting complexes were characterized by various spectroscopic techniques and in some cases using single crystal X-ray diffraction. The neutral pyrroles 4-H and 5-H react cleanly with [Mo(CO)6] to form the κP-coordinate complexes 4-H-Mo(CO)5 and 5-H-Mo(CO)5, respectively. IR spectroscopy of these complexes shows that C3-substitution barely changes the π-acceptor properties of the phosphine moiety. The η(5)-coordination was achieved when pyrrolides 4-K and 5-K were reacted with [Mn(CO)5Br] to give 4-Mn(CO)3 and 5-Mn(CO)3, respectively. The energy of the HOMOs in these three legged-piano stool complexes decreases on PPh2-substitution (5-Mn(CO)3) stabilizing the Mn-CO bonds, whereas the inverse effect is noticed for P(iPr)2-substitution (4-Mn(CO)3).

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“…Elemental analyses were performed by combustion and gas chromatographic analysis with an Elementar varioMICRO instrument. NaPyr t Bu 2 ( 1‐Na ),6a KPyr t Bu 2 Me 2 ( 2‐K ),19 and MnI 2 (thf) 3 ,20 were prepared according to the literature procedures.…”

Section: Methodsmentioning

confidence: 99%

The Missing Link: Manganese Complexes with Sterically Demanding Pyrrolyl Ligands

Kreye

Freytag

Daniliuc

et al. 2015

Zeitschrift anorg allge chemie

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Reaction of NaPyrtBu 2 [PyrtBu 2 = 2,5-(Me 3 C) 2 C 4 H 2 N] and KPyrtBu 2 Me 2 [PyrtBu 2 Me 2 = 2,5-(Me 3 C) 2 -3,4-Me 2 C 4 N] with MnI 2 (thf) 3 resulted in the isolation of the first bis(pyrrolyl)manganese(II) complexes. However, different coordination modes are realized depending on the identity of the Pyr-ligand. For example, the Mn II atom is κN coordinate in [(κN-PyrtBu 2 ) 2 Mn] (1-Mn), whereas several different species were isolated with the more bulky PyrtBu 2 Me 2 ligand. Depending on the reaction conditions the κN-coordinate complex [(κN-PyrtBu 2 Me 2 ) 2 Mn] (2-MnЈ) is initially formed, but converts on

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Sterically encumbered pyrrolyl ligands and their incorporation into the cycloheptatrienyl zirconium coordination sphere

Cited by 17 publications

References 95 publications

Pyrrole‐based pincer ligands containing iminophosphorane moieties and their coordination chemistry with group 1 metals and magnesium

Pyrrole‐based pincer ligands containing iminophosphorane moieties and their coordination chemistry with group 1 metals and magnesium

Phosphine-substituted sterically encumbered pyrrolyl ligands – synthesis and reactivity studies

The Missing Link: Manganese Complexes with Sterically Demanding Pyrrolyl Ligands

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