Mixed-Metal Metallocryptands. Short Metal−Metal Separations Strengthened by a Dipolar Interaction

Catalano, Vincent J.; Malwitz, Mark A.

doi:10.1021/ja048800n

Cited by 76 publications

(59 citation statements)

References 18 publications

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“…According to their theoretical studies, the short Au(I)-Ag(I) interactions arise from both an attractive ionic(dipolar) contribution and from dispersion-type correlation effects. We recently reported the mixed-metal metallocryptands [AuPdTl(P 2 phen) 3 ](PF 6 ) 2 and [AuPtTl(P 2 phen) 3 ](PF 6 ) 2 , where dipolar interactions shorten the M-Tl separations relative to those of their homometallic counterparts [22].…”

Section: Discussionmentioning

confidence: 99%

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Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Catalano

Etogo

2005

Journal of Organometallic Chemistry

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Section: Discussionmentioning

confidence: 99%

“…13 C { 1 H} NMR (125.7 MHz, CD 3 CN, 25°C) d = 183.57, 151.67, 150.16, 140.34, 125.73, 125.43, 124.87, 121.98, 39.49. (CH 3 CN) k max , nm (e): 210 (22,000), 264 (16,000).…”

Section: Preparation Of 1-methyl-3-(2-pyridinyl)-1h-imidazolium Hexafmentioning

confidence: 99%

Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Catalano

Etogo

2005

Journal of Organometallic Chemistry

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“…All of these geometric parameters are in agreement with a Pt-Tl bond. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] A noteworthy feature of this structure is the presence of o-F · · · Tl contacts, with distances Tl-F (15) ) 2.951(7) Å and Tl-F(20) ) 3.014(7) Å, which are in the range found in platinum(II) complexes containing Pt-Tl bonds, 19,22,23,27 or thallium complexes containing intra- [37][38][39][40] or intermolecular F · · · Tl contacts. 26,29,37,[41][42][43][44][45] These o-F · · · Tl contacts are also detected in solution in the 19 F NMR spectra of 5 (below).…”

Section: Halide Addition/abstraction In Phosphido Deriwatiwesmentioning

confidence: 99%

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

et al. 2008

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Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

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“…We have presented a self-assembled inorganic analogue of the bicyclophanes and, [22] specifically, the p-prismands. [20,23] The self-assembly strategy allows for increased yields in the macrobicyclization reaction and is a proof of principle of the design strategy to form arsenic-based supramolecular assem- Zuschriften blies from simple, identical starting compounds.…”

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Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex

2004

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The self-assembly of supramolecular coordination compounds has resulted in structures with a diverse range of properties, shapes, sizes, and stoichiometries, including helicates (M 2 L 2 , M 2 L 3 , etc.), triangles (M 3 L 3 ), squares (M 4 L 4 ), rings (e.g., M 6 L 6 ), and polyhedra (M 4 L 4 , M 4 L 6 , M 6 L 6 , M 8 L 12 , etc.).[1] These assemblies almost exclusively contain metals with square-planar, tetrahedral or octahedral coordination geometries. Metals that can exhibit more peculiar coordination geometries have typically been avoided as components for a supramolecular design strategy, [2] most likely because of their variable coordination spheres. Herein we describe a supramolecular design strategy for forming arsenic-based assemblies, which relies on the self-assembly of arsenic(iii) with thiol ligands-and hence the reversibility and lability of arsenic-sulfur bonds-and we report the first member of this class, [As 2 L 3 ] (H 2 L = a,a'-dimercapto-para-xylene). The design strategy incorporates the unusual, yet predictable trigonal-pyramidal coordination geometry of As III featuring a stereochemically active lone pair when coordinated by sulfurbased ligands (Figure 1 a). [3][4][5][6] We selected arsenic(iii) as a design component because of its unusual coordination geometry and a general lack of specific and powerful chelators for this highly toxic ion. [7] Arsenic compounds are legendary for their toxicity, and hydrated As III is recognized as a known human carcinogen. Arsenic is abundant in the earths crust and is all-toofrequently present as an environmental health hazard; [8][9][10] however, specific chelators for environmental and in vivo remediation and sensing applications are lacking. Furthermore, the stereochemically active lone pair of As III adds a novel feature to the targeted supramolecular assemblies: for instance, lone pairs directed into the cavity would provide a unique soft, Lewis-basic cavity environment (Figure 1 b). [11] Figure 1 illustrates the design strategy for forming C 3h -symmetric [As 2 L 3 ] assemblies, which is based on rigid, twofold symmetric dithiols capable of acting as bridging ligands. Dithiol ligand H 2 L[12] (Scheme 1) was the initial bridging ligand investigated, because it is easily prepared and thiolates show a well-known affinity for As III .[12] Using a ligand such as H 2 L allows for two possible orientations of the arsenic lone pairs: into or out of the cavity of the complex. Molecular models (CAChe, MM3) indicated that the lone pairs would be directed into the cavity with an AsÀAs distance of about 6 . [13] H 2 L, synthesized by a literature procedure, [12] forms a yellowish white solid in 52 % yield when treated with stoichiometric amounts of AsCl 3 and KOH in THF/methanol mixtures. The product has very simple 1 H and 13 C NMR spectra, indicative of formation of the desired high-symmetry C 3h complex, and the parent ion peak [H{As 2 L 3 }] + is present in the electrospray ionization mass spectrum. Interestingly, [As 2 L 3 ] also forms in the absence of any...

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Mixed-Metal Metallocryptands. Short Metal−Metal Separations Strengthened by a Dipolar Interaction

Cited by 76 publications

References 18 publications

Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex

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Mixed-Metal Metallocryptands. Short Metal−Metal Separations Strengthened by a Dipolar Interaction

Cited by 76 publications

References 18 publications

Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Luminescent coordination polymers with extended Au(I)–Ag(I) interactions supported by a pyridyl-substituted NHC ligand

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

Arsenic–π Interactions Stabilize a Self‐Assembled As2L3 Supramolecular Complex

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Arsenic–π Interactions Stabilize a Self‐Assembled As₂L₃ Supramolecular Complex