Ferrocenyl phosphane nickel carbonyls: Synthesis, solid state structure, and their use as catalysts in the oligomerization of ethylene

Schaarschmidt, Dieter; Kühnert, Janett; Tripke, Sascha; Alt, Helmut G.; Görl, Christian; Rüffer, Tobias; Ecorchard, Petra; Walfort, Bernhard; Lang, Heinrich

doi:10.1016/j.jorganchem.2010.03.012

Cited by 18 publications

(17 citation statements)

References 80 publications

(79 reference statements)

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“…Despite the marked, long‐standing impact of this work in organometallic chemistry and catalysis, it is all the more surprising that, as briefly cited, a CSD search (Cambridge Structural Database) revealed an astonishing scarcity of X‐ray data on Ni(CO) 3 (PR 3 ) complexes of commonly utilized, commercially available alkyl and aryl phosphines. Thus, some ferrocenylphosphine and fluoroalkylphosphine Ni(CO) 3 (PR 3 ) compounds have been characterized, among others, by X‐ray crystallography. In addition, carbonylation of a binuclear Ni I –Ni I complex of the p ‐terphenyl diphosphine 1,4‐bis(2‐(diisopropylphosphino)phenyl) benzene, afforded a crystalline material shown by X‐ray diffraction to be a mixture of nickel(0) carbonyls, in which 80 % of the phosphines are bound to Ni(CO) 2 and the remaining phosphines to Ni(CO) 3 .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Marín

Moreno

Navarro-Gilabert

et al. 2018

Chemistry A European J

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The experimental and computational characterization of a series of dialkylterphenyl phosphines, PR2Ar′ is described. The new P‐donors comprise five compounds of general formula PR2ArDtbp2 (R=Me, Et, iPr, c‐C5H9 and c‐C6H11); ArDtbp2 = 2,6‐C6H3‐(3,5‐C6H3‐(CMe3)2)2), and another five PR2Ar′ phosphines containing the bulky alkyl groups iPr, c‐C5H9 or c‐C6H11, in combination with Ar′=ArXyl2 , ArXyl'2 , or ArPh2 (L1–L10). Steric and electronic parameters have been determined computationally and from IR and X‐ray data obtained for the phosphines and for some derivatives, including tricarbonyl and dicarbonyl nickel complexes, Ni(CO)3(PR2Ar′) and Ni(CO)2(PR2Ar′). In the solid state, the free phosphines PR2Ar′ adopt one of the three possible structures formally related by rotation around the Cipso−P bond. Details on their relative energies and on the influence of the free phosphine structure on its coordination chemistry towards Ni(CO)n (n = 2, 3) fragments has been obtained by experimental and computational methods.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Marín

Moreno

Navarro-Gilabert

et al. 2018

Chemistry A European J

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“…Complex 28 displays moderate selectivity for butenes and low selectivity for 1-butene 73 , while complex 29 forms mainly butenes and hexenes with traces of octenes but with very low selectivity for alpha olefins (Table 5). 74 In the presence of MAO, the ferrocenyl phosphane nickel(0) complex 30 described by Lang et al 111 displays low activity and forms hexenes as the main product followed by butenes and higher oligomers (Table 5). Darkwa et al 112 suggest that the use of bulky ferrocenyl groups in pyrazolyl ligands may enhance catalyst stability and thus favor the activity of the catalytic system.…”

Section: Other Bidentate Neutral Ligandsmentioning

confidence: 99%

Nickel Catalyzed Olefin Oligomerization and Dimerization

et al. 2020

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Brought to life more than half a century ago and successfully applied for high-value petrochemical intermediates production, nickel-catalyzed olefin oligomerization is still a very dynamic topic, with many fundamental questions to address and industrial challenges to overcome. The unique and versatile reactivity of nickel enables the oligomerization of ethylene, propylene and butenes into a wide range of oligomers that are highly sought-after in numerous fields to be controlled. Interestingly, both homogeneous and heterogeneous nickel catalysts have been scrutinized and employed to do this. This rare specificity encouraged us to interlink them in this review so as to open up opportunities for further catalyst development and innovation. An in-depth understanding of the reaction mechanisms in play is essential to being able to fine-tune the selectivity and achieve efficiency in the rational design of novel catalytic systems. This review thus provides a complete overview of the subject, compiling the main fundamental/industrial milestones and remaining challenges facing homogeneous/heterogeneous approaches as well as emerging catalytic concepts, with a focus on the last 10 years.

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“…Herein, we report the synthesis of [ 1 ] according to Scheme where the reaction was performed using microwave heating where [Fe(CO) 5 ] acts as reductant and CO ligand source, similar to our previously described method . The final product can be crystallized directly from the reaction solution and the molecular structure of [ 1 ] agrees with the reported structure . The molecular structure of [ 1 ] showed d Fe‐Ni = 4.144 Å and torsion angle P1–C3–C8–P2 = 37.42° with tetrahedral coordination at the Ni atom (Figure ).…”

Section: Introductionmentioning

confidence: 55%

Section: Introductionmentioning

confidence: 99%

“…Lang et al reported the synthesis of [Ni(CO) 2 (dppf)] ([ 1 ]) from [Ni(CO) 4 ] and dppf and depending on the reaction conditions the dimeric complex [{Ni(CO) 3 } 2 (µ‐dppf)] or [ 1 ] could be made . Complex [ 1 ] was also be formed by heating the dimer [{Ni(CO) 3 } 2 (µ‐dppf)] to release [Ni(CO) 4 ] (Scheme ) . Another synthetic method was also described in the literature and it detailed the reduction of bis[tri(alkyl/phenyl)phosphino]nickel halides, such as [NiBr 2 (PCy 3 ) 2 ], with Na‐sand under a CO atmosphere complexes .…”

Section: Introductionmentioning

confidence: 99%

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Anodic Mechanism of 1,1′‐Bis(diphenylphosphino)ferrocenedicarbonylnickel Determined by Low‐Temperature Spectroelectrochemistry

Ringenberg

Döttinger

2019

Eur J Inorg Chem

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[Ni(CO)2(dppf)] [1] {dppf = 1,1′‐bis(diphenylphosphino)ferrocene} was made by reductive carbonylation of [NiCl2(dppf)] with [Fe(CO)5], similar to our recent report in Organometallics, 2019, 38, 586–592. Complex [1] showed two oxidation waves in the cyclic voltammogram. UV/Vis‐NIR spectroelectrochemistry (SEC) and IR SEC at –30 °C as well as computational support by means of DFT was used to assign the oxidation state of both metal atoms after oxidation. The monocation [1]+ showed a strong NIR absorption band which was described as an IVCT [NiI→FeII] and inverse IVCT (iIVCT) or hole transfer [FeII→NiI] based on time dependence DFT (TD‐DFT). The IR SEC spectrum of [1]+ showed multiple bands associated with two similar configurations, one which had the spin delocalized over both metal atoms and a second configuration where the spin is primarily Ni localized. The second oxidation to [1]2+ occurred at the Ni atom and resulted in release of a CO ligand followed by the formation of dimeric complex determined by low temperature IR SEC.

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Ferrocenyl phosphane nickel carbonyls: Synthesis, solid state structure, and their use as catalysts in the oligomerization of ethylene

Cited by 18 publications

References 80 publications

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Synthesis, Structure and Nickel Carbonyl Complexes of Dialkylterphenyl Phosphines

Nickel Catalyzed Olefin Oligomerization and Dimerization

Anodic Mechanism of 1,1′‐Bis(diphenylphosphino)ferrocenedicarbonylnickel Determined by Low‐Temperature Spectroelectrochemistry

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