Remote Activation of Nickel Complexes by Coordination of B(C6F5)3 to an Exocyclic Carbonitrile Functionality

Boardman, Brycelyn M.; Valderrama, Juan M.; Muñoz, Flor M.; Wu, Guang; Bazan, Guillermo C.; Rojas, René S.

doi:10.1021/om700933y

Cited by 43 publications

(21 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The influence of boron molecules with electrophilic character in remote activation of various nickel systems was previously reported [17][18][19][20][21] (Scheme 1), forming zwitterionic species that are probably responsible for more electropositive nickel, which finally makes the metal center more attractive to ethylene. Recently, we discovered a series of neutral methallyl nickel complexes (Scheme 2) able to polymerize or oligomerize ethylene using small amounts of co-activators such as B(C 6 F 5 ) 3 [22,23].…”

Section: Introductionmentioning

confidence: 88%

The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective

et al. 2015

View full text Add to dashboard Cite

In this work, global and local descriptors of chemical reactivity and selectivity are used to explain the differences in reactivities toward ethylene of methallyl nickel complexes and their B(C6F5)3 and BF3 adducts. DFT calculations were used to explain why nickel complexes alone are inactive in ethylene polymerization while their boron adducts can activate it. It is shown that chemical potential, hardness, electrophilicity and molecular electrostatic potential surfaces describe fairly well the reactivity and selectivity of these organometallic systems toward ethylene. Experimental data indicates that addition of a borane molecule to nickel complexes changes dramatically their reactivity-behavior that is confirmed computationally. Our results show that bare complexes are unable to activate ethylene-a Lewis base-because they also behave as Lewis bases. The addition of the co-catalyst-a Lewis acid-turns the adducts into Lewis acids, making them active towards ethylene.

show abstract

Section: Introductionmentioning

confidence: 88%

The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Lewis acidic tris(pentafluorophenyl)boron [B(C 6 F 5 ) 3 ] has been extensively used as a co‐catalyst in coordination polymerization of ethylene, and was also employed in the polymerization of NB [14, 10a] . Janiak and co‐workers reported that bidentate phosphate nickel and palladium complexes exhibited moderate catalytic activity in the presence of B(C 6 F 5 ) 3 /AlEt 3 , while most of the nickel and palladium complexes in this report did not polymerize NB with B(C 6 F 5 ) 3 or AlEt 3 alone .…”

Section: Introductionmentioning

confidence: 71%

Phosphine (oxide)‐(thio) phenolate palladium complexes: Synthesis, characterization and (co)polymerization of norbornene

Zhang

et al. 2017

Applied Organom Chemis

View full text Add to dashboard Cite

A series of palladium complexes (2a–2g) (2a: [6‐tBu‐2‐PPh2‐C6H3O]PdMe(Py); 2b: [6‐C6F5–2‐PPh2‐C6H3O]PdMe(Py); 2c: [6‐tBu‐2‐PPhtBu‐C6H3O]PdMe(Py); 2d: [2‐PPhtBu‐C6H4O] PdMe(Py); 2e: [6‐SiMe3–2‐PPh2‐C6H3O]PdMe(Py); 2f: [2‐tBu‐6‐(Ph2P=O)‐C6H3O]PdMe(Py); 2g: [6‐SiMe3–2‐(Ph2P=O)‐C6H3S]PdMe(Py)) bearing phosphine (oxide)‐(thio) phenolate ligand have been efficiently synthesized and characterized. The solid‐state structures of complexes 2d, 2f and 2g have been further confirmed by single‐crystal X‐ray diffraction, which revealed a square‐planar geometry of palladium center. In the presence of B(C6F5)3, these complexes can be used as catalysts to polymerize norbornene (NB) with relatively high yields, producing vinyl‐addition polymers. Interestingly, 2a/B(C6F5)3 system catalyzed the polymerization of NB in living polymerization manner at high temperature (polydispersity index 1.07, Mn up to 1.5 × 104). The co‐polymerization of NB and polar monomers was also studied using catalysts 2a and 2f. All the obtained co‐polymers could dissolve in common solvent.

show abstract

“…Ni complex with b-anilinoenolate ligand having a nitrile group (7e) also affords the zwitterionic complex by addition of B(C 6 F 5 ) 3 , which forms a C:N + -B(C 6 F 5 ) 3 -bonding. The produced complex catalyze ethylene polymerization without addition of co-catalyst [131]. Zwitterionic complex formed by the reaction of B(C 6 F 5 ) 3 with (2-(alkylideneamino or diphenylamino)benzoate)nickel complex (7f) promotes dimerization or polymerization depending on the N-substituents [132].…”

Section: Catalyst Having Tropone-imide Type Ligandsmentioning

confidence: 99%

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

Takeuchi

2014

Organometallic Reactions and Polymerization

View full text Add to dashboard Cite

Diimine Pd and Ni complexes catalyze the polymerization of ethylene, propylene, and a-olefins. The reaction involves isomerization of the growing terminal (chain walking) and, as its result, produces highly branched polyethylene and poy(a-olefin)s having a smaller number of the alkyl substituents than expected from the monomer structure. Ni complexes with salicylaldimine or iminocarboxamide ligands and Pd complexes with phosphinesulfonate ligands are used as single component catalysts for ethylene polymerization. Especially, the latter catalysts show tolerance towards polar functional groups and promote copolymerization of ethylene with wide varieties of polar monomers. The Pd and Ni complexes are able to catalyze ethylene polymerization in aqueous media to yield polyethylene particles. Fe and Co complexes with bis(imino)pyridine ligands show high catalytic activity for ethylene polymerization to yield linear polyethylene. Complexes of the metals such as Rh, Ir, Ru, and Ag were revealed to become catalytically active by proper design of the ligand. Not only monometallic complexes but also bimetallic or multimetallic complexes are used for ethylene polymerization. Late transition metal complexes catalyze selective cyclopolymerization of non-conjugated dienes and trienes to afford the polymers with cycloalkane groups with controlled stereochemistry.

show abstract

Remote Activation of Nickel Complexes by Coordination of B(C₆F₅)₃ to an Exocyclic Carbonitrile Functionality

Abstract: The synthesis of two new organometallic species, compounds 1 and 2, allows for the inVestigation of remote actiVation through an exocyclic CN functionality. The in situ generation of 2 from 1 plus excess B(C 6 F 5 ) 3 yields polyethylene possessing a bimodal distribution.

Cited by 43 publications

References 33 publications

The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective

The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective

Phosphine (oxide)‐(thio) phenolate palladium complexes: Synthesis, characterization and (co)polymerization of norbornene

Olefin Polymerization with Non-metallocene Catalysts (Late Transition Metals)

Contact Info

Product

Resources

About