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1.
J Am Chem Soc ; 145(40): 22222-22231, 2023 Oct 11.
Article in English | MEDLINE | ID: mdl-37782897

ABSTRACT

A cyclic alkyl(amino)carbene (CAAC)-stabilized 1,4-diborabenzene (DBB, 1) reacts with the group 10 precursor [Ni(CO)4] to yield the DBB pogo-stick complex [(η6-DBB)Ni(CO)] (2) as a dark-green crystalline solid. The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong π-donor properties of the DBB ligand. The reaction of 1 with [M(nbe)2] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(η6-DBB)M(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S0→S1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (dxz or dyz) to a d orbital located in the xy plane (dxy or dx2-y2), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2π* orbital destabilizes the DBB···Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe(CO)5] to yield the doubly CO-bridged M(0)→Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn-H addition with Ph3SnH to yield the corresponding Pt(II) stannyl hydride, [(η6-DBB)PtH(SnPh3)] (5).

2.
Chemistry ; 29(11): e202203345, 2023 Feb 21.
Article in English | MEDLINE | ID: mdl-36412126

ABSTRACT

The 2-aryl-3,4,5,6-tetraphenyl-1,2-azaborinines 1-EMe3 and 2-EMe3 (E=Si, Sn; aryl=Ph (1), Mes (=2,4,6-trimethylphenyl, 2)) were synthesized by ring-expansion of borole precursors with N3 EMe3 -derived nitrenes. Desilylative hydrolysis of 1- and 2-SiMe3 yielded the corresponding N-protonated azaborinines, which were deprotonated with nBuLi or MN(SiMe3 )2 (M=Na, K) to the corresponding group 1 salts, 1-M and 2-M. While the lithium salts crystallized as monomeric Lewis base adducts, the potassium salts formed coordination polymers or oligomers via intramolecular K⋅⋅⋅aryl π interactions. The reaction of 1-M or 2-M with CO2 yielded N-carboxylate salts, which were derivatized by salt metathesis to methyl and silyl esters. Salt metathesis of 1-M or 2-M with methyl triflate, [Cp*BeCl] (Cp*=C5 Me5 ), BBr2 Ar (Ar=Ph, Mes, 2-thienyl), ECl3 (E=B, Al, Ga) and PX3 (X=Cl, Br) afforded the respective group 2, 13 and 15 1,2-azaborinin-2-yl complexes. Salt metathesis of 1-K with BBr3 resulted not only in N-borylation but also Ph-Br exchange between the endocyclic and exocyclic boron atoms. Solution 11 B NMR data suggest that the 1,2-azaborinin-2-yl ligand is similarly electron-withdrawing to a bromide. In the solid state the endocyclic bond length alternation and the twisting of the C4 BN ring increase with the sterics of the substituents at the boron and nitrogen atoms, respectively. Regression analyses revealed that the downfield shift of the endocyclic 11 B NMR resonances is linearly correlated to both the degree of twisting of the C4 BN ring and the tilt angle of the N-substituent. Calculations indicate that the 1,2-azaborinin-1-yl ligand has no sizeable π-donor ability and that the aromaticity of the ring can be subtly tuned by the electronics of the N-substituent.

3.
Chemistry ; 27(43): 11226-11233, 2021 Aug 02.
Article in English | MEDLINE | ID: mdl-34008250

ABSTRACT

Boroles are attracting broad interest for their myriad and diverse applications, including in synthesis, small molecule activation and functional materials. Their properties and reactivity are closely linked to the cyclic conjugated diene system, which has been shown to participate in cycloaddition reactions, such as the Diels-Alder reaction with alkynes. The reaction steps leading to boranorbornadienes, borepins and tricyclic boracyclohexenes from the thermal reaction of boroles with alkynes are seemingly well understood as judged from the literature. Herein, we question the long-established mechanistic picture of pericyclic rearrangements by demonstrating that seven-membered borepins (i. e., heptaphenylborepin and two derivatives substituted with a thienyl and chloride substituent on boron) exist in a dynamic equilibrium with the corresponding bicyclic boranorbornadienes, the direct Diels-Alder products, but are not isolable products from the reactions. Heating gradually converts the isomeric mixtures into fluorescent tricyclic boracyclohexenes, the most stable isomers in the series. Results from mechanistic DFT calculations reveal that the tricyclic compounds derive from the boranorbornadienes and not the borepins, which were previously believed to be intermediates in purely pericyclic processes.

5.
Inorg Chem ; 59(15): 10866-10873, 2020 Aug 03.
Article in English | MEDLINE | ID: mdl-32672448

ABSTRACT

2,2'-Bipyridyl is shown to spontaneously abstract a borylene fragment (R-B:) from various hypovalent boron compounds. This process is a redox reaction in which the bipyridine is reduced and becomes a dianionic substituent bound to boron through its two nitrogen atoms. Various transition metal-borylene complexes and diboranes, as a well as a diborene, take part in this reaction. In the latter case, our results show an intriguing example of the homolytic cleavage of a B═B double bond.

6.
Angew Chem Int Ed Engl ; 59(31): 13109-13115, 2020 Jul 27.
Article in English | MEDLINE | ID: mdl-32329111

ABSTRACT

The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, π-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-π-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal π donation and without significant π/δ backbonding contributions.

7.
Chem Sci ; 11(2): 551-555, 2020 Jan 14.
Article in English | MEDLINE | ID: mdl-32206272

ABSTRACT

The addition of Lewis bases to a cyclic (alkyl)(amino)carbene (CAAC)-supported dihydroboron triflate yields the mixed doubly base-stabilised dihydroboryl cations [(CAAC)BH2L]+. Of these, [(CAAC)2BH2]OTf (OTf = triflate) underwent facile two-electron reduction with KC8 owing to a 1,2-hydride migration from boron to the carbene carbon to yield a stable hydroboryl anion. One-electron oxidation of the latter yielded the first neutral hydroboryl radical, which is bench-stable in the solid state.

8.
Chem Commun (Camb) ; 55(65): 9677-9680, 2019 Aug 21.
Article in English | MEDLINE | ID: mdl-31347619

ABSTRACT

The scandium Cp/COT hybrid sandwich compound [(η5-C5H5)Sc(η8-C8H8)] is resistant to metallation via conventional alkyllithium and lithium amide bases. In this work, clean, selective, stoichiometric and high-yielding mono- and dimetallation is accomplished using tandem trans-metal-trapping (TMT) involving LiTMP and iBu2AlTMP with deprotonation occurring selectively at the Cp and Cp/COT rings respectively, providing the first examples of selective metallation of a sandwich complex featuring a group 3 element.

9.
Angew Chem Int Ed Engl ; 58(13): 4405-4409, 2019 Mar 22.
Article in English | MEDLINE | ID: mdl-30719809

ABSTRACT

The lability of B=B, B-P, and B-halide bonds is combined in the syntheses of the first diiododiborenes. In a series of reactivity tests, these diiododiborenes undergo cleavage of all six of their central bonds in different ways, leading to products of B=B hydrogenation and dihalogenation as well as halide exchange.

10.
Angew Chem Int Ed Engl ; 57(33): 10752-10755, 2018 Aug 13.
Article in English | MEDLINE | ID: mdl-29785795

ABSTRACT

Diaryldihalodiboranes(4) were reacted with bis(amidinato)- and bis(guanidinato)silylenes to generate the first neutral diborane-centered radicals. These formally non-aromatic 5π electron systems are stable in the solid state as well as in solution and were characterized by solid-state structure determination, high-resolution mass spectrometry, and EPR spectroscopy. The reactivity of one of these radicals with the oxidant 1,4-benzoquinone led to ring-opening and B-O bond formation.

11.
Chemistry ; 24(10): 2403-2409, 2018 Feb 16.
Article in English | MEDLINE | ID: mdl-29363206

ABSTRACT

An improved, one-pot synthesis of the linear sandwich compound [Sc(η5 -C5 H5 )(η8 -C8 H8 )] is presented. The synthetic procedure is amenable to boryl- and silyl-substituted cyclopentadienyl and cyclooctatetraenyl ligands, thereby yielding the first functionalized derivatives. We found that the synthesis of the silyl-substituted mixed sandwich complexes produces higher yields when the ligand exchange is carried out stepwise, by isolating the intermediate trimethylsilylated half-sandwich complex [Sc(η8 -C8 H7 SiMe3 )Cl(THF)] (THF=tetrahydrofuran). The molecular structures of the parent complex, as well as of its mono-boryl-substituted derivatives, have been determined by single-crystal X-ray diffraction. In addition, the optical and electrochemical properties of the mixed sandwich complexes are reported.

12.
Chem Commun (Camb) ; 53(87): 11945-11947, 2017 Oct 31.
Article in English | MEDLINE | ID: mdl-29051948

ABSTRACT

Upon complexation to CuOTf, a PMe3-stabilized bis(9-anthryl) diborene slowly undergoes an intramolecular hydroarylation reaction at room temperature. Subsequent triflation of the B-H bond with CuOTf, followed by a PMe3 transfer, finally yields a cyclic sp2-sp3 boryl-substituted boronium triflate salt.

13.
Chemistry ; 23(50): 12210-12217, 2017 Sep 07.
Article in English | MEDLINE | ID: mdl-28326622

ABSTRACT

Sterically hindered, in situ generated 1,3,4-substituted 1,2,3-triazol-5-ylidene mesoionic carbenes (MICs) were employed to stabilize a number of aryl- and heteroaryldihaloboranes, as well as the first MIC-supported diborane. Reduction of borane adducts of the 1-(2,6-diisopropylphenyl)-3-methyl-4-tert-butyl-1,2,3-triazol-5-ylidene ligand with KC8 in non-coordinating solvents led to intramolecular C-H- and, C-C-activation at an isopropyl residue of the supporting ligand. DFT calculations showed that each of these activation reactions proceeds via a different isomer of a borylene intermediate.

14.
Chemistry ; 21(42): 14797-803, 2015 Oct 12.
Article in English | MEDLINE | ID: mdl-26387512

ABSTRACT

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa-bridging elements. Their preparation was achieved by salt-elimination reactions of the dilithiated precursor [Mn(η(5) -C5 H4 Li)(η(6) -C6 H5 Li)]⋅pmdta (pmdta=N,N,N',N',N''-pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single-atom-bridged derivatives, [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] and [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SiPh2 ], could also be determined by X-ray structural analysis. We investigated for the first time the reactivity of these ansa-cyclopentadienyl-benzene manganese compounds. The reaction of the distannyl-bridged complex [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )Sn2 tBu4 ] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn-Sn bond to give a triatomic ansa-bridge. The investigation of the ring-opening polymerization (ROP) capability of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] with [Pt(PEt3 )3 ] showed that an unexpected, unselective insertion into the Cipso -Sn bonds of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] had occurred.

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