Synthesis and Reactivity of Palladium Complexes Featuring a Diphosphinoborane Ligand

Synthetic access to the zerovalent palladium complexes {[(o-Ph2PC6H4)2BPh]­Pd­(L)} (L = pyridine (8a), 2,6-lutidine (8b)) is reported. Structural characterization and DFT analysis of 8a revealed a strong Pd→B interaction, which appears to inhibit oxidative addition reactions. Activation of allyl ace...

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Bibliographic Details
Published inOrganometallics Vol. 34; no. 10; pp. 1978 - 1984
Main Authors Schindler, Tobias, Lux, Marcel, Peters, Marius, Scharf, Lennart T, Osseili, Hassan, Maron, Laurent, Tauchert, Michael E
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 26.05.2015
Amer Chemical Soc
Subjects
Chemical Physics
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Physics
Science & Technology
CATALYSIS
HYDROGEN
TRANSITION-METAL-COMPLEXES
LEWIS-ACID
DATIVE SIGMA-BOND
BORON MOIETY
COORDINATION
AMBIPHILIC LIGAND
OXIDATIVE ADDITION
BORANE
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Summary:Synthetic access to the zerovalent palladium complexes {[(o-Ph2PC6H4)2BPh]­Pd­(L)} (L = pyridine (8a), 2,6-lutidine (8b)) is reported. Structural characterization and DFT analysis of 8a revealed a strong Pd→B interaction, which appears to inhibit oxidative addition reactions. Activation of allyl acetate is possible by reversible transfer of the acetate leaving group to the ligand’s borane functionality. Catalytic activity in the allylic substitution of allyl acetate with HNEt2 is sensitive to the presence of free acetate, which reduces borane inhibition by reversible borate formation.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.5b00217