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This work describes the synthesis and coordination behavior of a new mixed‐donor ligand PhC(NtBu)2SiC6H4PPh2 (1) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho‐lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ‐donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7, respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9. X‐ray analysis of 4 showed that the copper is in the spiro center of the two five‐membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2]−. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single‐crystal X‐ray diffraction studies. [ABSTRACT FROM AUTHOR]

We report the design, synthesis, structure, bonding, and reaction of a neutral 2π aromatic three‐membered disilaborirane. The disilaborirane is synthesized by a facile one‐pot reductive dehalogenation of amidinato‐silylene chloride and dibromoarylborane with potassium graphite. Despite the tetravalent arrangement of atoms around silicon, the three‐membered silicon‐boron‐silicon ring is aromatic, as evidenced by NMR spectroscopy, nucleus independent chemical shift calculations, first‐principles electronic structure studies using density functional theory (DFT) and natural bond orbital (NBO) based bonding analysis. Trimethylsilylnitrene, generated in situ, inserts in the Si−Si bond of disilaborirane to obtain a four‐membered heterocycle 1‐aza‐2,3‐disila‐4‐boretidine derivative. Both the heterocycles are fully characterized by X‐ray crystallography. [ABSTRACT FROM AUTHOR]

The cyclic alkyl(amino) carbene (cAAC) coordinated biradical of dimethylsilicon was isolated as (cAAC)2Me2Si (1), (cAAC = C(CH2)(CMe2)2N-2,6-i-Pr2C6H3), synthesized from the reduction of Me2SiCl2 using two equivalents of KC8 in the presence of two equivalents of cAAC. The reduction of Me2SiCl2 by one equivalent of KC8 in the presence of one equivalent of cAAC resulted in the stable dimethylsiliconchloride monoradical (cAAC)Me2SiCl (2). [ABSTRACT FROM AUTHOR]

Two novel cyclodiphosphazane cluster frameworks with Cu4X4 clusters as tetrahedral nodes and ferrocenyl cyclodiphosphazanes [Fe(η5-C5H4)2(PNtBu)2] as ditopic linkers have been synthesized. These frameworks having sodalite topology display a unique integration of porosity and redox activity and offer new opportunities for the synthesis of zeotype frameworks with soft phosphorus-based ligands. [ABSTRACT FROM AUTHOR]

To examine the steric effect of the phosphorus substituents in cyclodiphosphazanes, two less sterically demanding alkynyl-functionalized cis-[(μ-NtBuP)2(C=CPh)2] (1) and trans-[(μ-NtBuP)2(C=CPh)2] (2) were synthesized. The cis isomer 1, with a large subtending angle (135.8°) upon treatment with [Rh(CO)2Cl]2, afforded the first rhodium(I) cyclic pentameric macrocycle [Rh(CO)Cl{(μ-NtBuP)2(C=CPh)2}]5 (3). The crystal structure of the cyclic pentamer 3 closely resembles a classical "Ferris wheel". [ABSTRACT FROM AUTHOR]

The title diimidazolium salt was used together with Pd(OAc)2 to catalyze Suzuki--Miyaura and Heck reactions. The later gives mainly trans products. [ABSTRACT FROM AUTHOR]

A tetrafacial water-soluble molecular barrel (1) was synthesized by coordination driven self-assembly of a symmetrical tetrapyridyl donor (L) with a cis-blocked 90° acceptor [cis-(en)Pd(NO 3 ) 2 ] (en = ethane-1,2-diamine). The open barrel structure of (1) was confirmed by single crystal X-ray diffraction. The presence of a hydrophobic cavity with large windows makes it an ideal candidate for encapsulation and carrying hydrophobic drug like curcumin in an aqueous medium. The barrel (1) encapsulates curcumin inside its molecular cavity and protects highly photosensitive curcumin from photodegradation. The photostability of encapsulated curcumin is due to the absorption of a high proportion of the incident photons by the aromatic walls of 1 with a high absorption cross-sectional area, which helps the walls to shield the guest even against sunlight/UV radiations. As compared to free curcumin in water, we noticed a significant increase in solubility as well as cellular uptake of curcumin upon encapsulation inside the water-soluble molecular barrel (1) in aqueous medium. Fluorescence imaging confirmed that curcumin was delivered into HeLa cancer cells by the aqueous barrel (1) with the retention of its potential anticancer activity. While free curcumin is inactive toward cancer cells in aqueous medium at room temperature due to negligible solubility, the determined IC 50 value of ∼14 μM for curcumin in aqueous medium in the presence of the barrel (1) reflects the efficiency of the barrel as a potential curcumin carrier in aqueous medium without any other additives. Thus, two major challenges of increasing the bioavailability and stability of curcumin in aqueous medium even in the presence of UV light have been addressed by using a new supramolecular water-soluble barrel (1) as a drug carrier.