Structural and dynamic studies in solution of anionic dinuclear azolato-bridged palladium(II) complexes

Cruz, Raquel de la; Espinet, Pablo; Gallego, Ana M.; Martín‐Alvarez, José M.; Martínez‐Ilarduya, Jesús M.

doi:10.1016/s0022-328x(02)01772-2

Cited by 14 publications

(7 citation statements)

References 21 publications

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“…Irradiation of one of the signals simplifies the other to a sharp singlet, while at 323 K the signals appear as broad triplets. This spectroscopic and dynamic behavior has been reported in depth for other [PdRf 2 L 1 L 2 ] complexes. ,, …”

supporting

confidence: 76%

Observation of a Hidden Intermediate in the Stille Reaction. Study of the Reversal of the Transmetalation Step

et al. 2008

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supporting

confidence: 76%

Observation of a Hidden Intermediate in the Stille Reaction. Study of the Reversal of the Transmetalation Step

et al. 2008

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“…After only 20 min at room temperature, 14 was formed in 63% and 82% yield, respectively, as evidenced by the characteristic chemical shift of the ligated phosphine ( 31 P NMR) . The ease of formation of 14 from 15 and 16 is consistent with 14 being an off-cycle species, in which the catalyst mainly resides (Scheme ) …”

Section: Mechanistic Investigationmentioning

confidence: 91%

Suzuki-Miyaura Cross-Coupling of Unprotected, Nitrogen-Rich Heterocycles: Substrate Scope and Mechanistic Investigation

2013

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The Suzuki-Miyaura cross-coupling of unprotected, nitrogen-rich heterocycles using precatalysts P1 or P2 is reported. The procedure allows for the reaction of variously substituted indazole, benzimidazole, pyrazole, indole, oxindole and azaindole halides under mild conditions in good to excellent yields. Additionally, the mechanism behind the inhibitory effect of unprotected azoles on Pd-catalyzed cross-coupling reactions is described based on evidence gained through experimental, crystallographic, and theoretical investigations.

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“…Conversely, the consistency of the spectra even upon heating indicates that both isomers are rigid in solution. This is what is usually observed for dimethylpyrazolato‐bridged dimetallic complexes, in opposition to the less‐hindered pyrazolato‐bridged dinuclear species, where inversion of the central M(N–N) 2 M ring is often detected on the NMR time scale 17e,17f…”

Section: Resultsmentioning

confidence: 69%

Syntheses, Dynamic Behaviour and Theoretical Studies of [(Piperidinomethyl)silyl]methyl‐Cyclopalladated Dimetallic Complexes

et al. 2012

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The cationic complex [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )-κ 2 C,N}-(NCMe) 2 ]BF 4 (CH 2 NC 5 H 10 = piperidinomethyl) is obtained from the reaction of [Pd{CH 2 SiPh 2 (CH 2 NC 5 H 10 )-κ 2 C,N}(μ-Cl)] 2 with TlBF 4 in the presence of NCMe. It reacts with KO 2 CCH 3 leading to the dimetallic complex [Pd{CH 2 SiPh 2 -(CH 2 NC 5 H 10 )-κ 2 C,N}(μ-O 2 CCH 3 -κO:κЈO)] 2 , which exists only as the transoid isomer in solution. A dynamic process due to inversion of the acetato bridges is detected by variable-temperature 1 H NMR spectroscopy. The reaction of the same parent complex with Kdmpz (dmpz = dimethylpyrazolate) leads to the dinuclear complex [Pd{CH 2 SiPh 2 -(CH 2 NC 5 H 10 )-κ 2 C,N}(μ-dmpz-κN:κЈN)] 2 , which in solution exists as a mixture of cisoid and transoid isomers, but no inversion of the bridging pyrazolato groups has been observed.[a]

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Structural and dynamic studies in solution of anionic dinuclear azolato-bridged palladium(II) complexes

Cited by 14 publications

References 21 publications

Observation of a Hidden Intermediate in the Stille Reaction. Study of the Reversal of the Transmetalation Step

Observation of a Hidden Intermediate in the Stille Reaction. Study of the Reversal of the Transmetalation Step

Suzuki-Miyaura Cross-Coupling of Unprotected, Nitrogen-Rich Heterocycles: Substrate Scope and Mechanistic Investigation

Syntheses, Dynamic Behaviour and Theoretical Studies of [(Piperidinomethyl)silyl]methyl‐Cyclopalladated Dimetallic Complexes

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