Oxidative Addition of Boron Trifluoride to a Transition Metal

Bauer, Jürgen; Braunschweig, Holger; Kraft, Katharina; Radacki, Krzysztof

doi:10.1002/anie.201103226

Cited by 41 publications

(31 citation statements)

References 34 publications

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“…This is surprising due to the strong Lewis acid character of 2 and because reactions of electron‐rich transition‐metal bases with main‐group‐element Lewis acids have been widely studied . The oxidative addition of BF 3 to [(Cy 3 P) 2 Pt] ( 1 ), resulting in the difluoroboryl complex trans ‐[(Cy 3 P) 2 Pt(BF 2 )(FBF 3 )], and the synthesis of [(Cy 3 P) 2 Pt(BFAr F )][BAr Cl 4 ] (Ar F =3,5‐bis(trifluoromethyl)phenyl; Ar Cl =3,5‐dichlorophenyl) starting from 1 and Ar F BF 2 in the presence of Na[BAr Cl 4 ], are examples of such reactions . According to spectroscopic data, the formation of the Lewis pair [(Cy 3 P) 2 Pt→BF 2 Ar F ] constitutes the initial reaction step.…”

Section: Methodsmentioning

confidence: 99%

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Arnold

Bertermann

Bickelhaupt

et al. 2016

Chemistry A European J

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The reaction of PF with [(Cy P) Pt] gave the PF complex trans-[(Cy P) PtF(PF )][PF ], which was characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy, and elemental analysis. To the best of our knowledge, this reaction is the first example of the oxidative addition of a P-F bond to a transition metal and is a rare example of an activation of a main-group-element-fluorine bond by a metal. Relativistic DFT calculations showed that the formation of the Lewis pair [(Cy P) Pt→PF ], which was not observed even at low temperatures, represents the initial step of the reaction. From this key intermediate, the cation trans-[(Cy P) PtF(PF )] was furnished by a two-step mechanism involving, successively, a second and a third PF molecule.

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Section: Methodsmentioning

confidence: 99%

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Arnold

Bertermann

Bickelhaupt

et al. 2016

Chemistry A European J

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“…For 2:Pt ÀC1 1.973(3), PtÀP2 .2393 (7),N ÀC1 1.320(3);C1-Pt-P 172.55 (7). For 3:Pt ÀC1 1.86(3), PtÀP2 .239(1), N1ÀC1 1.25(4);C1-Pt-P 173.8 (10).For 4:Pt ÀB1 .960(4), PtÀC1 2.049(3), PtÀP2 .3491 (8), PtÀBr1 2.5968(3), C1ÀN1 .306(4);C1-Pt-P 166.12(9), B-Pt-Br1 170.1(1).For 5:Pt ÀB1 .986(4), PtÀC1 2.038(4), PtÀP2.340(1), PtÀBr12.6190(4), C1ÀN1 .309 (5);C1-Pt-P 166.4(1),B -Pt-Br1 169.80 (14). For 6:Pt ÀGa1 2.3962(3), PtÀC1 2.021(3), PtÀP2 .3227 (7), NÀC1 1.323(4);C1-Pt-P 169.83 (7), C1-Pt-Ga 91.32 (7), P-Pt-Ga 98.44(2).…”

Section: Reactivity Of Caac-containing Pt 0 Complexesmentioning

confidence: 99%

“…These complexes have already shown, for example, electrochemicala nd catalytic activity,a nd the ability to activate small molecules, such as dihydrogen and carbon dioxide. [3][4][5][6][7][8] Our entry into this field was motivatedb yadesire to prepare alternatives to the very useful and strongly Lewis basic complexes [Pt(PR 3 ) 2 ]( R= Et, iPr,C y) for variousp urposes,s uch as catalytic dehydrocoupling, [9] oxidative addition of EÀXb onds, [10] and the formation of metal-only Lewis pairs (MOLPs). [10e, 11] Herein, we describet he synthesis of both homoleptic [Pt(CAAC) 2 ]a nd heteroleptic zero-valent complexes of platinum and their reactivity towardsLewis acidic main-group compounds.…”

Section: Introductionmentioning

confidence: 99%

Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt⁰ Complexes

Arnold

Braunschweig

Brenner

et al. 2015

Chemistry A European J

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An improved synthetic route to homoleptic complex [Pt(CAAC(Me))2] (CAAC = cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAAC(Me))(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal-only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero-valent complexes were explored in concert with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC-containing Pt(0) complexes was investigated by TD-DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding π interactions between Pt and the CAAC carbon atoms.

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“…[6] There are only very few reports on insertion or addition reactions involving the BÀFb ond. [8] According to recent DFT calculations by Kameo and Sakaki, this reaction is endergonic and has al arge activation barrier if only one BF 3 molecule is involved. [7] Braunschweig et al observed that Lewisbasic platinum(0) complexes undergo oxidative additions into BF 3 .…”

mentioning

confidence: 99%

“…[7] Braunschweig et al observed that Lewisbasic platinum(0) complexes undergo oxidative additions into BF 3 . [8] According to recent DFT calculations by Kameo and Sakaki, this reaction is endergonic and has al arge activation barrier if only one BF 3 molecule is involved. As econd molecule of BF 3 is necessary to reduce the activation barrier and to make the reaction thermodynamically feasible.…”

mentioning

confidence: 99%

Activation of the B−F Bond by Diphenylcarbene: A Reversible 1,2‐Fluorine Migration between Boron and Carbon

et al. 2017

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Experiments in low-temperature matrices reveal that triplet diphenylcarbene inserts into the very strong BÀFb ond of BF 3 in atwo-step reaction. The first step is the formation of astrongly bound Lewis acid-base complex between the singlet state of diphenylcarbene and BF 3 .T his step involves an inversion of the spin state of the carbene from triplet to singlet. The second step requires visible-light photochemical activation to induce a1,2-F migration from boron to the adjacent carbon atom under formation of the formal insertion product of the carbene center into BF 3 .T he 1,2-F migration is reversible under short-wavelength UV irradiation, thus leading backt o the Lewis acid-base adduct.

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Oxidative Addition of Boron Trifluoride to a Transition Metal

Cited by 41 publications

References 34 publications

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt⁰ Complexes

Activation of the B−F Bond by Diphenylcarbene: A Reversible 1,2‐Fluorine Migration between Boron and Carbon

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Oxidative Addition of Boron Trifluoride to a Transition Metal

Cited by 41 publications

References 34 publications

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0Complex

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0Complex

Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt0 Complexes

Activation of the B−F Bond by Diphenylcarbene: A Reversible 1,2‐Fluorine Migration between Boron and Carbon

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Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt⁰Complex

Correlations and Contrasts in Homo‐ and Heteroleptic Cyclic (Alkyl)(amino)carbene‐Containing Pt⁰ Complexes