Synthesis and Electronic Structure of a Ferroborirene

Braunschweig, Holger; Fernández, Israel; Frenking, Gernot; Radacki, Krzysztof; Seeler, Fabian

doi:10.1002/anie.200700382

Cited by 69 publications

(41 citation statements)

References 51 publications

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“…79 Intriguingly, this methodology is also applicable to metallaborylene systems; reaction of (OC) 5 Cr[BFe(CO) 2 Cp*] with Me 3 SiCRCSiMe 3 leads to an analogous transfer of the borylene fragment, [BFe(CO) 2 Cp*] and to the formation of a unique ferroborirene system. 80 Transfer of the borylene ligand to an organic substrate via cycloaddition has also been demonstrated for cationic borylene complexes. Reaction of [CpFe(CO) 2 (BNCy 2 )] + [BAr f 4 ] À with 3,5-di-tert-butyl-o-benzoquinone generates the corresponding catechol derivative by a net [4+1] cycloaddition process.…”

Section: Borylene Transfer Chemistrymentioning

confidence: 99%

Transition metal borylene complexes: boron analogues of classical organometallic systems

2009

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In the ten years since the first examples of terminal borylene complexes were reported, rapid advances in the chemistry of this ligand class have been made, and parallels emerged with classical organometallic ligand systems (such as carbenes, vinylidenes and even CO) as well as with other subvalent main group ligand systems. This article reviews key developments in synthetic, structural and reaction chemistry, with particular attention focusing on recent discoveries in the field.

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Section: Borylene Transfer Chemistrymentioning

confidence: 99%

Transition metal borylene complexes: boron analogues of classical organometallic systems

2009

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“…1b) 45 . We have had an interest in borirenes for some time [46][47][48] , however, in our hands, B-aminoborirenes have so far been inactive towards lowvalent transition metals. The only known coordination chemistry of borirenes is the step-wise assembly of a η 3 :µ 3 -(2-methylborirene) unit on a Fe 3 (CO) 9 cluster core by Fehlner, suggesting a possible preference for π-coordination of borirenes to transition metals 49 .…”

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confidence: 96%

Unsupported boron–carbon σ-coordination to platinum as an isolable snapshot of σ-bond activation

et al. 2012

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σ-Complexes of transition metals-key intermediates in metal-mediated bond activation and homogeneous catalysis-have traditionally been isolable only when chelating or when one of the participating atoms is hydrogen. Here, by treating the Lewis-basic transition metal complex [Pt(PEt 3 ) 4 ] with an electron-poor borirene, we isolate a complex with an unsupported borirene ligand bound, not through the unsaturated C = C bond, but exclusively via a B-C single bond. using nmR spectroscopy, X-ray crystallography and density functional theory calculations, we show, herein, that coordination of the borirene ligand is based on electron donation from the B-C σ bond to the metal, aided by a strong Pt-to-B dative interaction. The complex is the first isolable non-agostic σ-complex featuring two p-block elements and has broad implications as a model for the metal-mediated activation of strong p-block-p-block σ-bonds.

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“…41 . While complex 5 has shown the capacity to transfer its (Z 5 -C 5 Me 5 )-(OC) 2 Fe-B: borylene fragment to alkynes to give borirenes, 42 its reactions involving polar multiple bond substrates are unexplored. While complex 5 has shown the capacity to transfer its (Z 5 -C 5 Me 5 )-(OC) 2 Fe-B: borylene fragment to alkynes to give borirenes, 42 its reactions involving polar multiple bond substrates are unexplored.…”

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Activation of boryl-, borylene and metalloborylene complexes by isonitriles

et al. 2015

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The reactions of isonitriles with a variety of metalloboryl and metalloborylene species are shown to yield a range of products, none of which display the typical Lewis acid-base reactivity previously observed between such metal complexes and other Lewis bases. Insertions of one, or several, isonitriles into the metal-boron bond give cyclic and spiro compounds with bonding controlled by the electron count at the metal and in the ring.

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Synthesis and Electronic Structure of a Ferroborirene

Cited by 69 publications

References 51 publications

Transition metal borylene complexes: boron analogues of classical organometallic systems

Transition metal borylene complexes: boron analogues of classical organometallic systems

Unsupported boron–carbon σ-coordination to platinum as an isolable snapshot of σ-bond activation

Activation of boryl-, borylene and metalloborylene complexes by isonitriles

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