Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates

Kim, Yong Joo; Jeon, Hyung-Tak; Lee, Kyung‐Eun; Lee, Soon W.

doi:10.1016/j.jorganchem.2010.06.013

Cited by 13 publications

(7 citation statements)

References 42 publications

(17 reference statements)

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“…The X-ray crystal structure of 6 reveals a square-planar coordination at the Pd(II) center, with cis-positioned methyl and PPh 3 groups, as well as a κ 2 conformation for N2S2 (Figure ). ,, The bond lengths of Pd–C (2.047 Å) and Pd–N ave (2.158 Å) are similar to (N2S2)Pd II Me 2 , and the Pd–P bond distance (2.250 Å) is also comparable to other reported values. , This conformation change of N2S2 from κ 3 to κ 2 in the presence of PPh 3 in 6 further confirms the possibility of a conformational change observed in the UV–vis spectra of 5 .…”

Section: Resultssupporting

confidence: 82%

“…35,41,42 The bond lengths of Pd−C (2.047 Å) and Pd−N ave (2.158 Å) are similar to (N2S2)Pd II Me 2 , and the Pd− P bond distance (2.250 Å) is also comparable to other reported values. 43,44 This conformation change of N2S2 from κ 3 to κ 2 in the presence of PPh 3 in 6 further confirms the possibility of a conformational change observed in the UV−vis spectra of 5.…”

Section: ■ Introductionsupporting

confidence: 69%

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Detection and Characterization of Mononuclear Pd(I) Complexes Supported by N2S2 and N4 Tetradentate Ligands

et al. 2020

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Palladium is a versatile transition metal used to catalyze a large number of chemical transformations, largely due to its ability to access various oxidation states (0, I, II, III, and IV). Among these oxidation states, Pd(I) is arguably the least studied, and while dinuclear Pd(I) complexes are more common, mononuclear Pd(I) species are very rare. Reported herein are spectroscopic studies of a series of Pd(I) intermediates generated by the chemical reduction at low temperatures of Pd(II) precursors supported by the tetradentate ligands 2,11-dithia[3.3](2,6)pyridinophane (N2S2) and N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane ( tBu N4): [(N2S2)Pd II (MeCN)] 2 (OTf) 4 (1), [(N2S2)-Pd II Me] 2 (OTf) 2 (2), [(N2S2)Pd II Cl](OTf) (3), [(N2S2)Pd II X](OTf) 2 (X = tBuNC 4, PPh 3 5), [(N2S2)Pd II Me(PPh 3 )](OTf) ( 6), and [( tBu N4)Pd II X 2 ](OTf) 2 (X = MeCN 8, tBuNC 9). In addition, a stable Pd(I) dinuclear species, [(N2S2)Pd I (μ-tBuNC)] 2 (ClO 4 ) 2 ( 7), was isolated upon the electrochemical reduction of 4 and structurally characterized. Moreover, the ( tBu N4)Pd I intermediates, formed from the chemical reduction of [( tBu N4)Pd II X 2 ](OTf) 2 (X = MeCN 8, tBuNC 9) complexes, were investigated by EPR spectroscopy, X-ray absorption spectroscopy (XAS), and DFT calculations and compared with the analogous (N2S2)Pd I systems. Upon probing the stability of Pd(I) species under different ligand environments, it is apparent that the presence of soft ligands such as tBuNC and PPh 3 significantly improves the stability of Pd(I) species, which should make the isolation of mononuclear Pd(I) species possible.

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Section: Resultssupporting

confidence: 82%

Section: ■ Introductionsupporting

confidence: 69%

Detection and Characterization of Mononuclear Pd(I) Complexes Supported by N2S2 and N4 Tetradentate Ligands

et al. 2020

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“…Control experiments involving the addition of PhNCS to [Ni(dcpe)(μ-S)] 2 resulted in the formation of 2, as shown by 31 P{ 1 H} NMR spectroscopy (Figure 2A). This indicates that either [Ni(dcpe)(μ-S)] 2 dimer formation is reversible or an intermolecular attack of the phenyl isothiocyanate on the bridging species occurs directly.…”

Section: ■ Discussionmentioning

confidence: 94%

“…The solvent was removed under reduced pressure, the solid extracted with benzene-d 6 , and the extract filtered through a pipet with glass wool into an NMR tube. 31 Preparation of Ni(dcpe)(κ 2 -S 2 C�NPh) (2). Phenyl isothiocyanate (14.4 mg, 0.106 mmol) was added to Ni(dcpe)(Ph)(SH) (3.6 mg, 0.017 mmol) in THF and allowed to react for 9 h. The volatiles were removed to yield 2.…”

Section: ■ Discussionmentioning

confidence: 99%

Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate

2022

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Nickel−sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ 2 -S 2 C�NPh) with the loss of benzene. The reaction was monitored by UV−visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH ⧧ and ΔS ⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ 2 -S 2 C�NPh), including a single-crystal X-ray structure determination, was achieved.

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“…Reductive elimination reactions that form Si–Si bonds are slightly rare. − The highly related rhodium complex [(dippe)Rh(μ-H)] 2 dehydrocouples secondary silanes by a mechanism that is virtually identical to the proposed stoichiometric dehydrocoupling by complex 4 [BAr f 4 ] . Study of silane dehydrocoupling using (1-Me-Ind)NiMe(PR 3 ) (Ind = indenyl, R = Ph, Cy, Me) by Fontaine and Zargarian supports a catalytic cycle similar to that in Scheme .…”

Section: Resultsmentioning

confidence: 99%

Element–Hydrogen Bond Activations at Cationic Platinum Centers To Produce Silylene, Germylene, Stannylene, and Stibido Complexes

2019

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Reactions of [(dippe)PtMe(Et 2 O)][BAr f 4 ] (4[BAr f 4 ], dippe = 1,2-bis(diisopropylphosphino)ethane; Ar f = 3,5-(CF 3 ) 2 C 6 H 3 ) with Mes 2 EH 2 (Mes = mesityl) liberate methane and produce silylene, germylene, or stannylene products [(dippe)Pt(H)EMes 2 ][BAr f 4 ] (E = Si, 1[BAr f 4 ]; Ge, 8; Sn, 9). In contrast, treatment of 4[BAr f 4 ] with tertiary silanes HSiR 3 (R = Ph, Et, OEt) failed to give the expected cationic silyl complexes but instead produced the bridging hydride [(dippe)Pt(μ-H)] 2 [BAr f 4 ] 2 (10) along with the corresponding disilane Si 2 R 6 . Complex 10 reacts with primary stibines RSbH 2 (R = Mes, dmp) to afford dimeric stibido complexes [(dippe)Pt(μ-SbHR)] 2 [BAr f 4 ] 2 (R = Mes, 11; dmp, 12) via Sb−H bond activation.

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Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates

Cited by 13 publications

References 42 publications

Detection and Characterization of Mononuclear Pd(I) Complexes Supported by N2S2 and N4 Tetradentate Ligands

Detection and Characterization of Mononuclear Pd(I) Complexes Supported by N2S2 and N4 Tetradentate Ligands

Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate

Element–Hydrogen Bond Activations at Cationic Platinum Centers To Produce Silylene, Germylene, Stannylene, and Stibido Complexes

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