The First η<sup>5</sup>-Indenylnickel Chelate Complexes with a Pendant Phosphane Tether

Hussain, Mazhar; Kohser, Stefanie; Janssen, Karin; Wartchow, Rudolf; Butenschön, Holger

doi:10.1021/om9004725

Cited by 16 publications

(22 citation statements)

References 63 publications

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Keywords: Arene ligands / Phosphane ligands / Transition metals / Chelates / Nickel

While phosphane-tethered cyclopentadienyl complexes with tertiary phosphane moieties have extensively been investigated for many metals, this is not the case for such complexes with a secondary phosphane tether. [13] While the tethers in chelates such as 1-6 bear electroneutral ligands, a smaller number of their anionic counterparts, alkoxido, amido, and phosphido chelates have also been reported. Here, we report the first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers.

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The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

Werner

Butenschön

2014

Eur J Inorg Chem

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Keywords: Arene ligands / Phosphane ligands / Transition metals / Chelates / NickelWhile phosphane-tethered cyclopentadienyl complexes with tertiary phosphane moieties have extensively been investigated for many metals, this is not the case for such complexes with a secondary phosphane tether. Only a few representatives of such complexes with early-transition-metals are known. Here, we report the first late-transition-metal cyclopentadienyl chelate complexes with silylphosphane or secondary phosphane tethers. The respective ligand system is generated by nucleophilic opening of spiro[2.4]hepta-4,6diene with lithium tert-butylphosphide. The anionic ligand is trapped with iron(II) chloride with formation of the respective ferrocene derivative. Treatment of lithium tert-butylphosphide with tert-butylchlorodimethylsilane or with chlorotriisopropylsilane affords the respective secondary silylphosphanes. Deprotonation, reaction with spiro[2.4]hepta-4,6diene, followed by treatment with nickel dihalide complexes www.eurjic.org FULL PAPER 1989; [9] 2 bears an internal amine ligand and was prepared by Hadjiliadis et al. in 1998; [10] 3 represents a cyclopentadienylalkylphosphane nickel chelate and was prepared in our group in 2007; [11] 4 is a cationic chelate with sulfur coordination, which was prepared by Rauchfuss et al. in 1985, [12] and alkene complex 5 was prepared by Okuda et al. in 1992. [7] Compared with cyclopentadienylalkyphosphane chelate complexes, the corresponding indenyl chelates are much less common. Recently, we prepared chelate 6 as the first nickel complex of its kind. [13] While the tethers in chelates such as 1-6 bear electroneutral ligands, a smaller number of their anionic counterparts, alkoxido, amido, and phosphido chelates have also been reported. Representative examples include zirconium(IV) complex 7 as an alkoxido chelate, which was prepared by Hermann et al., [14] and amido chelate 8, which was prepared by Erker et al. [15] Finally, Miyoshi, Nakazawa et al. provided a phosphido example in the form of complex 9 as a hafnium(IV) chelate (Scheme 2). [16] Compared with complexes such as 1-6, complexes such as 7-9 have been investigated to a much lesser extent. Scheme 2. Cyclopentadienyl chelate complexes with anionic tethers.In the context of our interest in cyclopentadienylalkylphosphane chelates of late-transition-metals such as cobalt [17][18][19][20][21][22][23][24][25][26][27][28][29] and nickel, [11,13] we noticed that phosphido chelates such as 9 are comparatively rare and known only for early-transition-metals such as group 4 metals, [15,[30][31][32][33] lanthanides, [34] or niobium. [35] One molybdenum example has been published by Scheer et al. [36] In many cases, these complexes were prepared by reaction of the dianionic ligand system with a suitable complexation reagent.While the reaction of a lithiated primary or secondary phosphane with a fulvene affords a ligand system with one carbon atom between the cyclopentadienyl and the phosphane moieties, [15,30,37] the corresponding rea...

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Keywords: Arene ligands / Phosphane ligands / Transition metals / Chelates / Nickel

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The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

Werner

Butenschön

2014

Eur J Inorg Chem

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“…Analogously, until now only one nickel allenylidene complex has been described by Butenschön et al [12]. We now report on the synthesis, the structural and the spectroscopic properties of a variety of nickel allenylidene complexes.…”

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Nickel alkynyl and allenylidene complexes: Synthesis and properties

Haas

Kaspar

Forner

et al. 2011

Journal of Organometallic Chemistry

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“…15 In the context of the present work 16 was treated with LiPtBuPh in THF at reflux for 3 d resulting in gave the indenyl chelate rac-18 as a diastereomeric mixture (10 : 1) in 71% yield. rac-18 is more air-sensitive as compared to the cyclopentadienyl chelate rac-12, so that attempts to remove a minor amount of the uncoordinated ligand were only partly successful.…”

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“…15,16 With the new tert-butylphenyl substituted ligand in hand, we prepared the respective nickel chelate rac-20 in 70% yield. rac-20 was characterized spectroscopically, all data are in accord with related complexes.…”

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“…rac-20 was characterized spectroscopically, all data are in accord with related complexes. 15,16 Jolly et al reported the synthesis of cyclopentadienylchromium dichloride chelates with a phosphane tether and their application as catalysts in alkene oligo-and polymerization reactions. 76 The complexes reported bear identical substituents at phosphorus, crystal structure analyses of the diphenyl and the dicyclohexyl complexes were included.…”

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New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

Janssen

Butenschön

2011

New J. Chem.

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The syntheses, characterization, and some reactions of (phosphanylethyl)cyclopentadienyl chelate complexes of cobalt, rhodium, iridium, nickel, and chromium with unsymmetrical substitution at the phosphorus atom are described. The ligand systems were prepared by nucleophilic ring opening of spiro[2.4]hepta-4,6-diene with lithium tert-butylphenylphosphide or lithium tert-butylcyclohexylphosphide. The anionic ligands give the respective chelate complexes by treatment with metal halide reagents. In three cases it was possible to obtain X-ray crystal structure analyses. The cobalt chelate complex undergoes oxidative addition with a dihydrosilane, the reaction results in the formation of products with three stereogenic centers at phosphorus, cobalt, and silicon, which show dynamic behavior as indicated by VTNMR. The rhodium chelate complex undergoes oxidative addition of iodomethane with diastereoselective formation of the respective Rh(III) chelate. While diastereoselectivity caused by a planar chiral indenyl ligand or by a stereogenic carbon center in the chelate backbone has earlier been observed, this is the first case of a stereoinduction by the stereogenic phosphorus ligand. Activation energies for the rotation of cobalt and rhodium chelates have also been determined by VTNMR.

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The First η⁵-Indenylnickel Chelate Complexes with a Pendant Phosphane Tether

Cited by 16 publications

References 63 publications

The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

Nickel alkynyl and allenylidene complexes: Synthesis and properties

New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

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The First η5-Indenylnickel Chelate Complexes with a Pendant Phosphane Tether

Cited by 16 publications

References 63 publications

The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

The First Late‐Transition‐Metal Cyclopentadienyl Chelate Complexes with Silylphosphane or Secondary Phosphane Tethers

Nickel alkynyl and allenylidene complexes: Synthesis and properties

New cyclopentadienylethylphosphane chelate complexes with unsymmetrical phosphane substitution

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The First η⁵-Indenylnickel Chelate Complexes with a Pendant Phosphane Tether