2017
DOI: 10.1002/anie.201700625
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An Intramolecular Silylene Borane Capable of Facile Activation of Small Molecules, Including Metal‐Free Dehydrogenation of Water

Abstract: The first single-component N-heterocyclic silylene borane 1 (LSi-R-BMes ; L=PhC(N Bu) ; R=1,12-xanthendiyl spacer; Mes=2,4,6-Me C H ), acting as a frustrated Lewis pair (FLP) in small-molecule activation, can be synthesized in 65 % yields. Its HOMO is largely localized at the silicon(II) atom and the LUMO has mainly boron 2p character. In small-molecule activation 1 allows access to the intramolecular silanone-borane 3 featuring a Si=O→B interaction through reaction with O , N O, or CO , and formation of silan… Show more

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Cited by 75 publications
(45 citation statements)
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“…The silicon center in 3 adopts a distorted tetrahedral geometry with a short Si−O distance of 1.557(4) and 1.537(4) Å in accordance with related four‐coordinated Lewis acid stabilized silanones (1.531–1.579 Å) containing a Si=O double bond . The Si−O distance is only slightly elongated when compared with recently reported genuine silanones (1.518–1.537 Å) .…”
Section: Methodssupporting
confidence: 77%
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“…The silicon center in 3 adopts a distorted tetrahedral geometry with a short Si−O distance of 1.557(4) and 1.537(4) Å in accordance with related four‐coordinated Lewis acid stabilized silanones (1.531–1.579 Å) containing a Si=O double bond . The Si−O distance is only slightly elongated when compared with recently reported genuine silanones (1.518–1.537 Å) .…”
Section: Methodssupporting
confidence: 77%
“…Recently, Braun and co‐workers used a silylene–borane Lewis adduct as a tool for trapping a single water molecule, affording a zwitterionic silanol stabilized by intramolecular hydrogen bonds . In 2017, our group reported the first intramolecular silylene–borane FLP which activates H 2 , O 2 , CO 2 and even dehydrogenates water yielding a borane‐stabilized silanone E with a dative Si=O→B bond . Herein, we present the synthesis of the bis(silylene–borane) adduct 2 with the ferrocene spacer and its mild oxidation with CO 2 yielding the first borane‐stabilized bis(silanone) adduct 3 .…”
Section: Methodsmentioning
confidence: 99%
“… Reactivity of water towards low‐valent silicon compounds; Mes=2,4,6‐trimethylphenyl; IPr=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene …”
Section: Methodssupporting
confidence: 80%
“…A characteristic downfield shifted singlet for the ammonium protons was found in the 1 H NMR spectrum of 6 at δ =12.56 ppm. The 11 B{ 1 H} NMR spectrum exhibits one sharp singlet at δ =−6.8 ppm, which compares well with boronates or oxygen‐bound boranes . The 1 H, 29 Si HMBC NMR spectrum revealed a resonance at δ =−58 ppm in the 29 Si domain.…”
Section: Methodsmentioning
confidence: 99%
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