Stereochemical investigations of coordinated sulfur stereocenters. X-ray structures of diastereomers of (-)589-[Pd{(R)-CH3CH(1-C10H6)NMe2-C2,N}(R/S)-{Ph2PCH2SMe-P,S}]PF6

Chooi, Simon Y.M.; Hor, Tsa; Leung, Pak‐Hing; Mok, K. F.

doi:10.1021/ic00034a033

Cited by 57 publications

(31 citation statements)

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“…The role of the N-substituents seems not to 60°): nearly equal 3 J HCNH constant values have to be prebe very significant in this case, in contrast with the assumpdicted for both NH protons in the λ(S) conformation and tion made previously. [58] [59] different values only for the δ(S) skew-envelope. The differ-Unfortunately, no information could be found regarding ence in the predicted values of the 3 J HCNH constant may the 4 J HCP constant for the α-methine proton of related αserve as a basis of the reliable criteria for identification of Me-substituted palladacycles based on primary arylalkylthe axial and equatorial NH protons in the palladacycles amines; usually this signal was described as a mulderived from primary and secondary benzylamines.…”

Section: Structure Of Complexes 1a؊4a In Solutionmentioning

confidence: 99%

Steric Promotion of Aromatic C–H Bond Activation in Primary Benzylamines

Dunina¹,

Кузьмина

Kazakova

et al. 1999

Eur. J. Inorg. Chem.

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ortho‐Palladation of a sterically crowded primary benzylamine, α‐phenylneopentylamine, was accomplished in a moderate yield of 50% in the reaction with the weakest of palladation agents (Li2PdCl4) under very mild conditions, due to a steric promotion of an aromatic C–H bond activation. The structure of dimer 1a thus formed and the palladacycle conformation were established on the basis of 1H‐NMR spectroscopy of its mononuclear derivatives with [D5]pyridine (3a) and triphenylphosphane (4a), and an X‐ray investi‐gation of the latter.

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Section: Structure Of Complexes 1a؊4a In Solutionmentioning

confidence: 99%

Steric Promotion of Aromatic C–H Bond Activation in Primary Benzylamines

Dunina¹,

Кузьмина

Kazakova

et al. 1999

Eur. J. Inorg. Chem.

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“…The structure of solvate 10· 3/2C 2 H 4 Cl 2 is shown in Figure , and the pertinent geometric data are given in Table . Comparison of the structural parameters determined for the parent complex 8· AcOEt and the cationic bis(chelate) complex 10 revealed a slight but statistically significant elongation of the Pd–N and Pd–C25 bonds in the latter complex (naturally, the Pd–S bond is also longer than the Pd–Cl bond in 8 ). Furthermore, the formation of a second chelate ring in 10 results in an opening of the P–Pd–S/Cl angle and a closure of the adjacent N–Pd–S/Cl angle by approximately 5°, whereas the remaining interligand angles remain practically unchanged.…”

Section: Resultsmentioning

confidence: 97%

Palladium(II) Complexes of Homologated Ferrocene Phosphanylether and Thioether Ligands

et al. 2017

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The reaction of [1′‐(diphenylphosphanyl)ferrocenyl]methanol/borane (1:1) with in situ formed N,N,N′,N′,S‐pentamethylisothiouronium iodide and sodium hydride, followed by removal of the borane protecting group with 1,4‐diazabicyclo[2.2.2]octane, afforded 1‐(diphenylphosphanyl)‐1′‐[(methylthio)methyl]ferrocene (3) as a new, homologated, hybrid phosphanylferrocene ligand. Compound 3 and the congeneric phosphanyl ether 2 were studied as ligands in PdII complexes. When treated with [PdCl2(MeCN)2] in a Pd/ligand ratio of 1:1, compound 3 furnished a mixture of two Pd complexes, including the ligand‐bridged dimer [{µ(P,S)‐3}PdCl2]2 (6), which was structurally characterized. Upon increasing the amount of ligand to 2 equiv., a similar reaction produced the bis(phosphane) complex [PdCl2(3‐κP)2] (7). Bridge‐cleavage reactions of the dipalladium complex [(LNC)Pd(µ‐Cl)]2 {LNC = 2‐[(dimethylamino‐κN)methyl]phenyl‐κC1} with donors 3 and 2 proceeded in a uniform manner to give the corresponding phosphane complexes [(LNC)PdCl(3‐κP)] (8) and [(LNC)PdCl(2‐κP)] (9). Conversely, removing the Pd‐bonded chloride from these complexes with AgClO4 generated the bis(chelate) complex [(LNC)Pd(3‐κ2P,S)] (10) and the aqua complex [(LNC)Pd(H2O)(2‐κP)] (11), respectively, both of which could be converted back into their precursors by adding Bu4NCl. The structures of the complexes 6–11 (some in solvated form) were determined by single‐crystal X‐ray diffraction analysis.

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“…The primary amines 1-phenylethylamine and 1-(4-methylphenyl)ethylamine were cyclopalladated and converted to chloro-bridged dinuclear complexes by well-established methods [16,17]. Related dinuclear compounds, mostly naphtyl rather than phenyl derivatives, have been used successfully for resolution via formation of diastereomers [18][19][20][21]. The chloro-bridged intermediates were cleaved by the silver carboxylates (Scheme 1) in the presence of ethylendiamine (en).…”

Section: Resultsmentioning

confidence: 99%