Catalytic Activity of [2]Borametallocenophanes

Braunschweig, Holger; Dörfler, Rainer; Friedrich, Maria; Kraft, Mario; Öechsner, Andreas

doi:10.1002/zaac.201100315

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Synthesis Structure and Bonding Of Diboron(4) Compounds1

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“…The B–B bond in [2]-borametalloarenophanes has been cleaved by addition to alkynes using palladium and platinum catalysts, inserting the carbon–carbon triple bond into the B–B bridge. − Braunschweig and co-workers were also able to isolate heterobimetallic compounds resulting from oxidative addition of the B–B bond to a platinum(0) compound (Scheme , right). ,,, Reaction with B 2 pin 2 or B 2 cat 2 resulted in boryl exchange and loss of the B–B bridge (Scheme , left) . Additionally, these complexes were found to be active catalysts in ethylene polymerization and ethylene/1-hexene copolymerization. , …”

Section: Synthesis Structure and Bonding Of Diboron(4) Compoundsmentioning

confidence: 99%

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

et al. 2016

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Section: Synthesis Structure and Bonding Of Diboron(4) Compoundsmentioning

confidence: 99%

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

et al. 2016

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Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis

G. Alférez,

Moreno,

Gaona

et al. 2023

ACS Catal.

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The incorporation of boron functionalities into transition-metal catalysts has become a promising strategy to improve catalytic performance, although their synthesis typically entails the preparation of sophisticated bifunctional ligands. We report here the facile and direct postsynthetic functionalization of rhodium(I) compound [(η 5 -C 9 H 7 )Rh(PPh 3 ) 2 ] (1) by treatment with perfluorinated boranes. Borane addition to 1 results in an unusual C(sp 2 )-H hydride migration from the indenyl ligand to the metal with the concomitant formation of a C−B bond. In the case of Piers' borane [HB(C 6 F 5 ) 2 ], this is followed by a subsequent hydride migration that leads to an unprecedented 1,2-hydrogen shift reminiscent of Milstein's cooperative dearomatization pathways. Computational investigations provide a mechanistic picture for the successive hydride-migration steps, which enriches the noninnocent chemistry of widespread indenyl ligands. Moreover, we demonstrate that the addition of Piers' borane is highly beneficial for catalysis, increasing catalyst efficiency up to 3 orders of magnitude.

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Catalytic Activity of [2]Borametallocenophanes

Cited by 2 publications

References 33 publications

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis

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