A simple route to dinuclear complexes containing unusual μ-<i>N</i><sub>sulfonamido</sub> bridges

Sanmartín‐Matalobos, Jesús; Portela-García, Cristina; Fondo, Matilde; García‐Deibe, Ana M.; Llamas-Saíz, Antonio L.

doi:10.1080/00958972.2016.1161183

Cited by 5 publications

(7 citation statements)

References 35 publications

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“…29 The first directing group (C1-based ligand) binds to the palladium centre (Pd1) in a tridentate C , N , N ′ fashion utilising C1, the imine nitrogen N4, and the sulfonamide nitrogen anion (N7), the latter of which also binds to Pd2. 30 , 31 This binding mode is consistent with the imine and sulfonamide acting as a bidentate directing group. By contrast, the other imine (C21-based ligand), coordinates to Pd2 through C21 and the imine nitrogen (N24) only.…”

Section: Resultsmentioning

confidence: 56%

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

2017

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Section: Resultsmentioning

confidence: 56%

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

2017

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“…The Pd-N sulphonamide distances (in the range 2.057(3)-2.103(3) Å are longer than the Pd-N imine ones. This fact evidences some lability for µ 2 -N bridges is evidenced [24,25]. This is a highly valued structural feature in catalysis because the break of the Pd-N sulphonamide bound could allow the access of a substrate to the reaction site.…”

Section: Crystal Structure Of H2sbmentioning

confidence: 64%

“…The main geometric parameters of this compound are listed in Table S4. Coordination distances Pd-O and Pd-N are ranging 1.971(2)-1.972(2) Å and 2.022(3)-2.103(3) Å, respectively, so they can be considered within the usual ranges found for other related compounds [24,25,34]. By contrast, Pd-O tosyl distances are longer (3.035(2) and 3.129(2) Å), what reflects very weak metal-ligand interactions, so that they cannot be qualified as true coordination bonds.…”

Section: Crystal Structure Of H2sbmentioning

confidence: 84%

“…Despite this potential interest, very little research has been devoted to the synthesis of dinuclear palladium(II) complexes through µ 2 -N bridges with short contacts. Thus, a search in Cambridge Structural Database data [15] indicates that, among more than a million of crystal structures already deposited, only eleven dinuclear palladium complexes connected through µ 2 -N bridges display Pd-Pd distances shorter than 3.02 Å [16][17][18][19][20][21][22][23][24][25]. Figure 1 shows the four types of µ 2 -N bridges so far reported in literature.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we have reported the crystal structures of two dinuclear palladium(II) complexes, with Pd-Pd distances in the range 3.00-3.02 Å [24,25]. These short interatomic distances were achieved by using tridentate Schiff bases that simultaneously bind two Pd 2+ ions through µ 2 -N sulphonamido bridges.…”

Section: Introductionmentioning

confidence: 99%

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Taking Advantage of the Coordinative Behavior of a Tridentate Schiff Base Ligand towards Pd2+ and Cu2+

et al. 2019

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We have explored the suitability of an O,N,N-donor Schiff base (H 2 SB) for obtaining dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids). Spectroscopic studies demonstrated that the complexation of H 2 SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. We have found two square planar centers with Pd-N-Pd angles of 93.08(11) • and a Pd-Pd distance of 3.0102(4) Å in Pd 2 (SB) 2 ·Me 2 CO. This Pd-Pd distance is 30% shorter than the sum of the van der Waals radii, which is in accordance with a strong palladophilic interaction. Fluorescence studies on H 2 SB-M 2+ interaction showed that H 2 SB can detect Cu 2+ ions in a sample matrix containing various metal ions (hard, soft, or borderline acids) without interference. Determination of binding constants showed that H 2 SB has a greater affinity for borderline acids than for soft acids.Crystals 2019, 9, 407 2 of 15 obtaining dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids) through a double µ 2 -N sulphonamido bridge (Figure 1 , right). Spectroscopic studies demonstrated that the complexation of H 2 SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. The crystal structure of Pd 2 (SB) 2 ·Me 2 CO, which has been elucidated by using single crystal X-ray diffraction techniques, has shown a Pd-Pd distance of 3.0102(4) Å, which is sensibly shorter than the sum of the van der Waals radii (4.30 Å). This latter value corresponds to that deduced from recent statistical analyses of intermolecular contacts in deposited X-ray crystal structures, paying also special attention to homoatomic contacts involving Pd, Pt, Cu, Ag, and Au [26]. Fluorescence studies on the interaction of H 2 SB towards heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Cd 2+ , and Pd 2+ revealed the ability of H 2 SB to detect Cu 2+ in aqueous solutions containing various metal ions (hard, soft, or borderline acids) without interference. Determination of binding constants showed that H 2 SB has a greater affinity for borderline acids than for soft acids.Crystals 2019, 9, x FOR PEER REVIEW 2 of 15 dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids) through a double μ2-Nsulphonamido bridge (Figure 1, right). Spectroscopic studies demonstrated that the complexation of H2SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. The crystal structure of Pd2(SB)2·Me2CO, which has been elucidated by using single crystal X-ray diffraction techniques, has shown a Pd-Pd distance of 3.0102(4) Å, which is sensibly shorter than the sum of the van der Waals radii (4.30 Å). This latter value corresponds to that deduced from recent statistical analyses of intermolecular contacts in deposited X-ray crystal structures, paying also special a...

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Exploration of an easily synthesized fluorescent probe for detecting copper in aqueous samples

et al. 2017

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An easily synthesized fluorescent probe for detecting copper in aqueous samples, with a short response time and at neutral pH, has been investigated. Through the chelation of Cu ions or by binding to CuO nanoparticles, the fluorescence emission of the 2-(aminomethyl)aniline derivative HL is quenched by over 50%. Spectroscopic determination of the association constants of HL with some metal ions showed that the ligand has a higher affinity toward Cu than toward other d-block metal ions. The comparative bonding ability of the aniline-based fluorescent probe in d-block metal complexes was studied in solution by a combination of UV-Vis, H NMR and mass spectrometry analyses. Besides these, the bonding behavior has been investigated in the solid state by X-ray diffraction, FT-IR spectroscopy and elemental analysis. The crystal structures of Pd(L) and Co(L)(HL)(HO) were elucidated.

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A simple route to dinuclear complexes containing unusual μ-N_sulfonamido bridges

Cited by 5 publications

References 35 publications

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

Taking Advantage of the Coordinative Behavior of a Tridentate Schiff Base Ligand towards Pd2+ and Cu2+

Exploration of an easily synthesized fluorescent probe for detecting copper in aqueous samples

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A simple route to dinuclear complexes containing unusual μ-Nsulfonamido bridges

Cited by 5 publications

References 35 publications

Single operation palladium catalysed C(sp3)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

Single operation palladium catalysed C(sp3)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

Taking Advantage of the Coordinative Behavior of a Tridentate Schiff Base Ligand towards Pd2+ and Cu2+

Exploration of an easily synthesized fluorescent probe for detecting copper in aqueous samples

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Product

Resources

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A simple route to dinuclear complexes containing unusual μ-N_sulfonamido bridges

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups

Single operation palladium catalysed C(sp³)–H functionalisation of tertiary aldehydes: investigations into transient imine directing groups