Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

Son, Jung‐Ho; Pudenz, Michael A.; Hoefelmeyer, James D.

doi:10.1039/c0dt00798f

Cited by 44 publications

(31 citation statements)

References 81 publications

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“…This interaction seems similar in nature to those described for 4 and 5, and to other similar sandwich complexes [13,[26][27][28]30] but in the case of 6 the shorter Ag-C distance (2.433(3) Å) corresponds to the carbon atom adjacent to the bzq C ipso (C(16)), also with a relatively short distance involving this C ipso (C(17), 2.516(3) Å). These structural parameters seem to point in this case to a di-hapto Agbzq interaction, a common feature found for complexes containing silver and aromatic rings [12,[70][71][72]. The absence of a second PtAg bond for the silver center could be responsible for this di-hapto configuration versus the mono-hapto found in the trinuclear sandwich complexes.…”

Section: Reactivity Of 1-3 Toward Agclomentioning

confidence: 82%

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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Luminescent complexes a b s t r a c t Complexes [Pt(C 6 F 5 )(bzq)(CNR)] {R = t Bu (1), 2-naphthyl (2), 2,6-Me 2 Ph (3)} have been prepared by replacement of the labile acetone in [Pt(C 6 F 5 )(bzq)(Me 2 CO)] with the corresponding isocyanide ligand. The structures 1 and 3 (X-ray) confirms their square planar geometry, with the bzq ligand coplanar to the metal plane. The reactions of 1-3 toward AgClO 4 lead to the trinuclear complexes [{Pt(C 6 F 5 ) (bzq)(CNR)} 2 Ag]ClO 4 {R = t Bu (4), 2-naphthyl (5)} or the tetranuclear [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6). The structures of these three polynuclear complexes have been established by X-ray diffraction studies. Two pseudo-polymorphs of 4 (4a and 4b), only differing in the crystallization solvent, have been found. 4a/b and 5 are trinuclear Pt-Ag-Pt complexes with a ''sandwich'' disposition. In all three cases, two ''Pt(C 6 F 5 )(bzq)(CNR)'' fragments are linked by a silver atom through Pt ? Ag bonds of donor acceptor nature and the silver center establishes a short g 1 interaction with the C ipso of the bzq ligands. Furthermore, the study of the structure of 6 reveals two ''(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph)PtAg'' subunits, each containing a Pt ? Ag bond related by an inversion center and held together through g 2 interactions established by the silver atom of one unit and one of the aromatic rings of the bzq ligand of the other. The reaction of 1-3 with [Ag(OClO 3 )(PPh 3 )] produces [(C 6 F 5 )(bzq)(CNR)PtAg(PPh 3 )]ClO 4 {R = t Bu, (7), 2-naphthyl (8), 2,6-Me 2 Ph (9)}. These dinuclear clusters contain a Pt ? Ag bond and show dynamic processes in solution (NMR) which involve the rupture and formation of these interactions. The X-ray structure of 7 confirms the presence of a Pt-Ag bond and a g 1 interaction with the C ipso of the bzq ligand (2.514(6) Å). All the crystal structures determined show pÁ Á Áp interactions of the bzq which stack in a parallel fashion with interplanar distances of ca. 3.3-3.4 Å. In 5 and 6 the aromatic fragments of the isocyanide ligands also take part in these pÁ Á Áp interactions. Absorption and emission properties of all the complexes 1-9 have been studied and explained with the aid of TD-DFT theoretical calculations.Compounds 1-9 are not emissive in solution but they are in rigid matrix. In glassy 2-Me-THF or CH 2 Cl 2 at 77 K the Pt/Ag compounds 4-9 at any concentration (10 À3 M, 10 À4 M, 10 À5 M) show the same emission spectra as their corresponding starting complexes 1-3, in line with the rupture of the Pt-Ag bonds. In the solid state only the dinuclear compounds [Pt(C 6 F 5 )(bzq)(CN-t Bu)AgPPh 3 ]ClO 4 (7) and [Pt(C 6 F 5 )(bzq) (CN-2,6-Me 2 Ph)AgPPh 3 ]ClO 4 (9) together with the tetranuclear complex [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6) are emissive at room temperature showing bright greenish (7, 9) or yellowish (6) phosphorescence. In all three compounds a significant contribution of M 0 orbitals (AgPPh 3 /Ag) to the frontier orbitals (FO) has been observed, and their main emissions see...

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Section: Reactivity Of 1-3 Toward Agclomentioning

confidence: 82%

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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“…[20] Complexes featuring acyclic boron-containing p-ligands are relatively scarce, [21] and complex 1'-Pd represents a rare example of a h 4 -boratabutadiene complex. [22] The exact mechanism for the transformation of 1-Pd into 1'-Pd remains unclear at this stage, [23] but there are a few precedents for such concomitant Ar À X and phosphine ligand C À H activation.…”

Section: Resultsmentioning

confidence: 99%

ortho‐(Dimesitylboryl)phenylphosphines: Positive Boryl Effect in the Palladium‐Catalyzed Suzuki–Miyaura Coupling of 2‐Chloropyridines

Malacea¹,

Chahdoura²,

Devillard³

et al. 2013

Adv Synth Catal

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Catalytic systems combining ortho-(dimesitylboryl)phenylphosphines and palladium precursors have been evaluated in the Suzuki-Miyaura couplings of chloro-N-heterocycles, in particular 2-chloroA C H T U N G T R E N N U N G pyridines, with arylboronic acids. The Lewis basic character of the substrates does not interfere with the Lewis acidic site of the ligands, even for a substrate featuring free NH 2 groups. The influence of several reaction parameters has been studied and the ortho-dimesitylboryl moiety was actually found to substantially enhance the catalytic performance. The role of this group has been examined using preformed phosphine-borane/Pd complexes and the formation of an original phosphine/h 4 -boratabutadiene complex has been identified as a possible deactivation pathway. Regioselective coupling of 2,6-dichloro-3-nitropyridine with phosphine-borane/Pd catalysts has also been explored, and sequential double cross-couplings were found to give a direct and efficient access to unsymmetrical 2,6-diarylpyridines.

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“…All reagents were purchased from commercial sources and used without further purification. 8-Iodoquinoline was prepared according to the literature [12]. All 1 H and 13 C NMR spectra were recorded using a Varian 200 MHz NMR spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…M. p. 252-254 °C. The synthesis of 3·H 2 O has been reported previously [12,15]. A solution of 1 (100 mg, 0.4 mmol) in 3 mL acetonitrile was prepared and kept in a capped vial in ambient conditions.…”

Section: Synthesis Of (Quinolinium-8-yl) Trihydroxyborate (2)mentioning

confidence: 99%

“…Simultaneously inspired by the work with 8-quinolylboronic acid and recent developments in frustrated Lewis pair chemistry [9][10][11], and as part of our ongoing efforts to study pre-organized frustrated Lewis pairs [12][13][14], we embarked to prepare 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-quinoline (1). In this report, we show that 1 is readily hydrolyzed to the zwitterionic (quinolinium-8-yl)trihydroxyborate (2) or a dimeric anhydride 8,16-dihydroxy-8,16-epoxy [1,5,2,6]diazadiborocino [1,8,7-ij:5,4,3-i′j′]diquinoline (3), depending on the reaction conditions (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Hydrolysis of 8-(pinacolboranyl)quinoline: where is the 8-quinolylboronic acid?

Son

Tamang

Yarbrough

et al. 2015

Zeitschrift Für Naturforschung B

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The compound 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-quinoline was prepared and found to hydrolyze rapidly in air; however, the expected product (quinolin-8-yl)boronic acid was not observed. Instead, the (quinolinium-8-yl)trihydroxyborate zwitterion or an anhydride were observed depending on the conditions of hydrolysis. The two products are related to one another in the degree of hydration, and the two forms could be interconverted. Both hydrolysis products were structurally characterized. Additionally, a commercial sample of '8-quinolylboronic acid' was actually found to be the anhydride. The results call into question whether monomeric (quinolin-8-yl)boronic acid can actually be isolated in the neutral Lewis base-free form.

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Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

Cited by 44 publications

References 81 publications

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

ortho‐(Dimesitylboryl)phenylphosphines: Positive Boryl Effect in the Palladium‐Catalyzed Suzuki–Miyaura Coupling of 2‐Chloropyridines

Hydrolysis of 8-(pinacolboranyl)quinoline: where is the 8-quinolylboronic acid?

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