Synthesis and Reactivity of Palladium Complexes Featuring a Diphosphinoborane Ligand

Schindler, Tobias; Lux, Marcel; Peters, Marius; Scharf, Lennart T.; Osseili, Hassan; Maron, Laurent; Tauchert, Michael E.

doi:10.1021/acs.organomet.5b00217

Cited by 66 publications

(43 citation statements)

References 36 publications

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“…Tauchert has more recently observed rare E-E 0 bond activations in which the C-O bond in various allyl substrates were added across a palladium-boron bond (Scheme 21). 71 The complexes utilised for these formal oxidative additions were zerovalent palladium complexes bearing the Z 2 -BC-Ph DPB Ph ligand where the fourth coordination site at the metal centre was occupied by a pyridine or 2,6-lutidine ligand. The C-O bond activations occurred at room temperature over the course of 1-20 h depending on the allyl species utilised.…”

Section: Element-element Bond Cleavage (Those Not Involving Hydrogen)mentioning

confidence: 99%

Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds

Owen

2016

Chem. Commun.

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This feature article examines some of the recent advances in the chemistry of Z-type transition metal-borane and X-type transition metal-boryl complexes. It focuses on the employment of these boron-based functionalities acting as stores and transfer agents for functional groups such as hydrides, alkyl groups and aryl groups which can either be abstracted or delivered to the metal centre. The review also explores the rather novel reactivity involving the cleavage of H-H, E-H and E-E' bonds (where E and E' are a range of groups) across the transition metal-boron bond in such complexes. It explores the early examples of the addition of H-H across transition metal-borane bonds and describes the new transformation in the context of other known modes of hydrogen activation including classic oxidative addition and heterolytic cleavage at transition metal centres as well as Frustrated Lewis Pair chemistry. Similar reactivity involving transition metal-boryl complexes are also described particularly those which undergo both boryl-to-borane and borane-to-borohydride transformations. The delivery of hydride to the metal centre in combination with the potential to regenerate the borohydride functional group via a recharging process is explored in the context of providing a new strategy for catalysis. Finally, a light-hearted look at the analogy of the 'stinging processes' involving Trofimenko type ligands is taken one step further to determine whether it is indeed in the nature of scorpionate ligands to repeatedly 'sting' just as the real life scorpions do.

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Section: Element-element Bond Cleavage (Those Not Involving Hydrogen)mentioning

confidence: 99%

Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds

Owen

2016

Chem. Commun.

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“…Also, Figueroa and co‐workers synthesized a platinum–borane complex and applied it to H–H, O–H, and N–H σ‐bond activations 31. More recently, Tauchert and co‐workers synthesized a palladium–borane complex and succeeded in the C–O σ‐bond cleavage of allyl acetate 32. Based on these successful reports, one can expect that this type of transition‐metal complex with Z‐type ligands will become more important in the catalytic chemistry of transition‐metal complexes in the near future.…”

Section: Participation Of the Lewis Acid In Stoichiometric σ‐Bond Actmentioning

confidence: 99%

Cooperative Catalysis of Combined Systems of Transition‐Metal Complexes with Lewis Acids: Theoretical Understanding

Guan

Zeng

Kameo

et al. 2016

The Chemical Record

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The combination of transition-metal complexes and Lewis acids has been recently applied to several catalytic reactions, in which the Lewis acid plays a crucial role as a non-innocent additive to accelerate the reaction. In this review article, the reasons for the acceleration by the Lewis acid are discussed based on our recent theoretical studies. In the H-H σ-bond activation of a dihydrogen molecule by a nickel(0)-borane complex, the empty p orbital of the borane moiety interacts with the H-H σ bonding MO to form charge transfer (CT) from the dihydrogen molecule to the borane moiety to accelerate the reaction. In the B-F σ-bond activation of BF by a platinum(0)-bisphosphine complex, the second BF molecule interacts with the F atom that is dissociating from the B atom to stabilize the transition state and product by the CT from the F atom to the second BF . In this reaction, the substrate BF plays a crucial role as the Lewis acid to accelerate the activation of the B-F σ bond. In the nickel-catalyzed decyanative coupling of arylcarboxybenzonitriles with acetylenes, two molecules of the aluminum Lewis acid interact with the cyano N atom and the carbonyl O atom of the substrate to stabilize the transition state and intermediate. In the nickel-catalyzed alkylation of aromatic amides with alkenes, the Lewis acid enhances the para regioselectivity of alkylation by interacting with the carbonyl O atom. In the nickel-catalyzed carboxylation of sp carbon and sp carbon atoms with carbon dioxide, not the σ-bond activation but the insertion reaction of carbon dioxide into the metal-carbon bond is accelerated by the Lewis acid by interacting with the O atom of carbon dioxide, because the CT from the metal-carbon bond to carbon dioxide is enhanced by the interaction. This theoretical knowledge suggests that the combination of transition-metal complex and Lewis acid can broaden the application range of transition-metal complex as catalyst.

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“…Unfortunately, all the tested complexes feature apparently too strong Rh→B interactions to be displaced by methyl acetate and no reaction occurred. In a quite related study, Tauchert recently prepared Pd(0) PBP complexes 17 and studied oxidative additions 18. Phenyl bromide failed to react but allyl acetate was activated, affording the zwitterionic Pd allyl complex 18 with the acetate bound to boron (formal addition of the allyl-OAc bond across the Pd→B interaction).…”

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confidence: 99%

Complexes of ambiphilic ligands: reactivity and catalytic applications

2016

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Since the mid 2000's, the incorporation of Lewis acid moieties in ligands for transition metals has been studied extensively. So-called ambiphilic ligands were shown to possess rich and unusual coordination properties and special focus was given to the coordination of Lewis acids as σ-acceptor ligands (concept of Z-type ligands). Recent studies have demonstrated that the presence of Lewis acids at or nearby transition metals can also strongly impact their reactivity. These results are surveyed in this review. The stoichiometric transformations and catalytic applications of complexes deriving from ambiphilic ligands are presented. The different roles the Lewis acid can play are discussed.

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Synthesis and Reactivity of Palladium Complexes Featuring a Diphosphinoborane Ligand

Cited by 66 publications

References 36 publications

Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds

Functional group migrations between boron and metal centres within transition metal–borane and –boryl complexes and cleavage of H–H, E–H and E–E′ bonds

Cooperative Catalysis of Combined Systems of Transition‐Metal Complexes with Lewis Acids: Theoretical Understanding

Complexes of ambiphilic ligands: reactivity and catalytic applications

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