trans-[Ni(Me3Ph)(NHPh)(PMe3)2], a Monomeric NiII–Amide Complex

VanderLende, Daniel D.; Boncella, James M.; Abboud, Khalil A.

doi:10.1107/s0108270194011534

Cited by 5 publications

(1 citation statement)

References 7 publications

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“…Single crystals for X-ray diffraction were obtained from a diethyl ether solution stored at −35 °C. The solid-state molecular structure of 10 (Figure ) confirms that the ligand remains bound in a κ 3 -manner, and the nickel–nitrogen bond length of 1.9383(6) Å is comparable to that in other terminal nickel amido complexes (ranging from 1.812(3)–1.932(3) Å), albeit on the longer end which we rationalize as due to steric congestion around the nickel center. ,,− ,,,− The aryl group on the amido ligand is oriented perpendicular to the PPC ligand, and the overall geometry of 10 is distorted square planar geometry with τ 4 = 0.25.…”

Section: Resultsmentioning

confidence: 53%

Ancillary Ligand Modification via Reductive Elimination at Nickel(II)

Zimmerman

Fryzuk

2019

Organometallics

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The nickel(II) complex [κ3-BnPPC]NiBr (1), stabilized by an orthometalated-phosphine benzyl group and two bulky phosphine donors, results in facile reductive elimination with certain organometallic reagents that can attain the η3-bonding mode. Thus, the reaction of diphenylmethyllithium with 1 produces the Ni(0) derivative [κ2-BnPP(η2-CHPh2)]Ni (4), which forms as a single diastereomer and displays an η2-phenyl moiety. Similarly, reaction of benzylpotassium with 1 results in the analogous nickel(0) complex [κ2-BnPP(η2-CH2Ph)]Ni, albeit less cleanly. Reaction of 1 with allylmagnesium chloride also results in reductive elimination to generate the Ni(0) species [κ2-BnPP(η2-CH2CHCH2)]Ni. In contrast, reaction with trimethylsilylmethyllithium generates the stable Ni(II) derivative, [κ3-BnPPC]Ni(CH2SiMe3), which can only be induced to undergo clean reductive elimination by heating to 80°C in the presence of ethylene. Similarly, the bulky 2,6-di-iso-propyl-phenylamidolithium reacts with 1 to give the stable Ni(II) species [κ3-BnPPC]Ni(NH-2,6-iso-Pr2C6H3), which upon thermolysis in the presence of ethylene results in a mixture of products. It is proposed that facile reductive elimination occurs only for those hydrocarbyl groups that can attain a transient η3-bonding mode that accelerates this process due to the formation of an 18-electron intermediate.

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Section: Resultsmentioning

confidence: 53%

Ancillary Ligand Modification via Reductive Elimination at Nickel(II)

Zimmerman

Fryzuk

2019

Organometallics

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Synthesis and Crystal Structures of Monomeric Diamidonickel(II) Complexes

Lee

Peng

Kui

et al. 2000

Eur. J. Inorg. Chem.

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The thermally stable nickel(II) diamides [NiL2] [L = −N(SiMe3)(8‐C9H6N) (1), −N(SitBuMe2)(8‐C9H6N) (2)] have been synthesized from the reaction of NiCl2 with the appropriate lithium amide. X‐ray crystallography revealed that the amido ligands bind in a chelating manner, forming a distorted tetrahedral environment around the nickel center. Complexes 1 and 2 have magnetic moments of 3.05 and 2.74 μB, respectively, which indicate a d8 electronic configuration with two unpaired electrons.

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Nickel–Carbon σ-Bonded Complexes

Cámpora

2007

Comprehensive Organometallic Chemistry III

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trans-[Ni(Me3Ph)(NHPh)(PMe3)2], a Monomeric NiII–Amide Complex

Cited by 5 publications

References 7 publications

Ancillary Ligand Modification via Reductive Elimination at Nickel(II)

Ancillary Ligand Modification via Reductive Elimination at Nickel(II)

Synthesis and Crystal Structures of Monomeric Diamidonickel(II) Complexes

Nickel–Carbon σ-Bonded Complexes

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