The First Boron–Tellurium Double Bond: Direct Insertion of Heavy Chalcogens into a Mn=B Double Bond

Liu, Siyuan; Légaré, Marc‐André; Auerhammer, Dominic; Hofmann, Alexander; Braunschweig, Holger

doi:10.1002/anie.201708729

Cited by 46 publications

(42 citation statements)

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“…This angle is about 20°larger than the Os−S−B angle in the borothiolate compounds OsH(SBR 2 )(η 2 -H 2 )(CO)(P i Pr 3 ) 2 (113−119°). 17 This is consistent with that observed by Braunschweig and co-workers for the M−chalcogene−B angle, in the borachalcogene complexes Cp(CO) 2 Mn[EB t Bu-(IMe)] (E = S, Se, Te), which increases by going up in the group, i.e., in the sequence Te < Se < S. 18 However, in contrast to the Braunschweig's compounds, the O1−B bond length of 1.332(6) Å reveals a short chalcogene−boron single bond. 19 The DFT optimized structure (Figure 1b) confirms the trihydride character of the OsH 3 unit, although the calculated separations between H01 and H02 and between H02 and H03 of 1.57 and 1.64 Å, respectively, suggest the presence of weak nonclassical interactions between the hydride ligands.…”

Section: ■ Results and Discussionsupporting

confidence: 88%

Reactions of an Osmium(IV)-Hydroxo Complex with Amino-Boranes: Formation of Boroxide Derivatives

et al. 2018

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The discovery of a reaction which allows preparation of boroxide complexes of platinum group metals and study of their behavior under CO atmosphere is described. The trihydride-osmium(IV)-hydroxo complex OsH 3 (OH){κ 3-P,O,P-[xant(P i Pr 2) 2 ]} (1, xant(P i Pr 2) 2 = 4,5-bis-(diisopropylphosphino)xanthene) reacts with the amino-boranes i Pr(H)NBCy 2 and i Pr(H)NBBN to give the osmium(IV)boroxide derivatives OsH 3 (OBR 2){κ 3-P,O,P-[xant(P i Pr 2) 2 ]} (BR 2 = BCy 2 (2), BBN (3); BBN = 9-borabicyclo[3.5.1]nonane) and i PrNH 2 as a consequence of the addition of the O−H bond of the hydroxo ligand of 1 to the B−N bond of the amino-boranes. At room temperature under CO atmosphere, complexes 2 and 3 eliminate H 2 to afford the osmium(II)− boroxide compounds OsH(OBR 2)(CO) 2 {κ 2-P,P-[xant(P i Pr 2) 2 ]} (BR 2 = BCy 2 (4), BBN (5)) bearing a κ 2-P,P-coordinated ether-diphosphine. The subsequent reductive elimination of the borinic acids R 2 BOH needs heating and a long duration and leads to the tricarbonyl-osmium(0) derivative Os(CO) 3 {κ 2-P,P-[xant(P i Pr 2) 2 ]} (6) with the phosphorus atoms of the diphosphine lying in the equatorial plane of a pentagonal bypyramid of donor atoms around the metal center. In contrast to 2 and 3, under CO atmosphere, precursor 1 eliminates water to initially give the trans-dihydride OsH 2 (CO){κ 3-P,O,P-[xant(P i Pr 2) 2 ]} (7), which subsequently evolves to the cis-dihydride-cis-dicarbonyl derivative OsH 2 (CO) 2 {κ 2-P,P-[xant-(P i Pr 2) 2 ]} (8) and finally into the tricarbonyl 6.

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Section: ■ Results and Discussionsupporting

confidence: 88%

Reactions of an Osmium(IV)-Hydroxo Complex with Amino-Boranes: Formation of Boroxide Derivatives

et al. 2018

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“…2.03 Å) and the slightly wider B–E–B angle ( 6 : 56.9(2); 7 : 51.31(18)°). Unlike the IMe-supported dithienyldiborene 13 or the manganese-bound borylene [Cp(OC) 2 Mn B t Bu(IMe)] (Cp = cyclopentadienyl), 20 neither compound I or II showed any reactivity toward elemental tellurium in toluene, even after prolonged heating in benzene at 80 °C.…”

Section: Resultsmentioning

confidence: 99%

Closely related yet different: a borylene and its dimer are non-interconvertible but connected through reactivity

et al. 2018

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“…The other two classes of borylenes have recently been authoritatively reviewed and continue to attract considerable interest. [230][231][232][233][234][235][236] Figure 20. Orbitals relevant to substrate activation in both borylenes and TM complexes.…”

Section: Boron(i) Systemsmentioning

confidence: 99%

Metallomimetic Chemistry of Boron

2019

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The study of main-group molecules that behave and react similarly to transition metal (TM) complexes has attracted significant interest in the recent decades. Most notably, the attractive idea of eliminating the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of many TM complexes that arise from combinations of empty and filled d-orbitals and that seem ideally suited to bind and activate many substrates. In this Review, we look at boron, an element which, despite its non-metal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in inter-element cooperative systems, diboron molecules and hypovalent complexes, the fifth element can acquire a truly metallomimetic character. As we discuss, this character is particularly strikingly demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

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The First Boron–Tellurium Double Bond: Direct Insertion of Heavy Chalcogens into a Mn=B Double Bond

Cited by 46 publications

References 58 publications

Reactions of an Osmium(IV)-Hydroxo Complex with Amino-Boranes: Formation of Boroxide Derivatives

Reactions of an Osmium(IV)-Hydroxo Complex with Amino-Boranes: Formation of Boroxide Derivatives

Closely related yet different: a borylene and its dimer are non-interconvertible but connected through reactivity

Metallomimetic Chemistry of Boron

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