A bis(PCN) palladium pincer complex with a remarkably planar 2,5-diarylpyrazine core.

A bimetallic Pd complex of a bis(pincer) with a diarylpyrazine core has been prepared. The complex demonstrates near-perfect coplanarity of the aromatic core, is fluorescent under UV irradiation, and displays two quasi-reversible reduction events.

Site specific redox properties in ligand differentiated di-nickel complexes inspired by the acetyl CoA synthase active site.

Bimetallic transition metal complexes with site-specific redox properties offer a versatile platform for understanding electron polarization, intramolecular electron transfer processes, and customizing electronic and magnetic properties that might impact reactivity and catalyst design. Inspired by the dissymmetric nickel sites in the Acetyl CoA Synthase (ACS) Active Site, three new bimetallic Ni(N2S2)-Ni(S2C2R2) complexes based on Ni(N2S2) metalloligand donor synthons, Nid, in mimicry of the nickel site distal to the redox-active iron sulfur cluster of ACS, and nickel dithiolene receiver units, designated as Nip, the nickel proximal to the 4Fe4S cluster, were combined to explore the influence of ligand environment on electronic structure and redox properties of each unit. The combination of synthons gave a matrix of three S-bridged dinickel complexes, characterized by X-ray crystallography, and appropriate spectroscopies. Computational modeling is connected to the electronic characteristics of the nickel donor and receiver units. This study demonstrated the intricacies of identifying sites of electrochemical redox processes, within multi-metallic systems containing non-innocent ligands.

Copper-mediated cyclization of thiosemicarbazones leading to 1,3,4-thiadiazoles: Structural elucidation, DFT calculations, in vitro biological evaluation and in silico evaluation studies.

Cancer's global impact necessitates innovative and less toxic treatments. Thiosemicarbazones (TSCs), adaptable metal chelators, offer such potential. In this study, we have synthesized N (4)-substituted heterocyclic TSCs from syringaldehyde (TSL1, TSL2), and also report the unexpected copper-mediated cyclization of the TSCs to form thiadiazoles (TSL3, TSL4), expanding research avenues. This work includes extensive characterization and studies such as DNA/protein binding, molecular docking, and theoretical analyses to demonstrate the potential of the as-prepared TSCs and thiadiazoles against different cancer cells. The DFT results depict that the thiadiazoles exhibit greater structural stability and reduced reactivity compared to the corresponding TSCs. The docking results suggest superior EGFR inhibition for TSL3 with a binding constant value of - 6.99 Kcal/mol. According to molecular dynamics studies, the TSL3-EGFR complex exhibits a lower average RMSD (1.39 nm) as compared to the TSL1-EGFR complex (3.29 nm) suggesting that both the thiadiazole and thiosemicarbazone examined here can be good inhibitors of EGFR protein, also that TSL3 can inhibit EGFR better than TSL1. ADME analysis indicates drug-likeness and oral availability of the thiadiazole-based drugs. The DNA binding experiment through absorption and emission spectroscopy discovered that TSL3 is more active towards DNA which is quantitatively calculated with a Kb value of 4.74 × 106 M-1, Kq value of 4.04 × 104 M-1and Kapp value of 5 × 106 M-1. Furthermore, the BSA binding studies carried out with fluorescence spectroscopy showed that TSL3 shows better binding capacity (1.64 × 105 M-1) with BSA protein. All the compounds show significant cytotoxicity against A459-lung, MCF-7-breast, and HepG2-liver cancer cell lines; TSL3 exhibits the best cytotoxicity, albeit less effective than cisplatin. Thiadiazoles demonstrate greater cytotoxicity than the TSCs. Overall, the promise of TSCs and thiadiazoles in cancer research is highlighted by this study. Furthermore, it unveils unexpected copper-mediated cyclization of the TSCs to thiadiazoles.

Host-guest interactions of coumarin-based 1,2-pyrazole using analytical and computational methods: Paper strip-based detection, live cell imaging, logic gates and keypad lock applications.

A novel Coumarin-based 1,2-pyrazole, HCPyTSC is synthesised and characterized. The chemosensor has been shown to have efficient colourimetric and fluorescence sensing capabilities for the quick and selective detection of fluoride and copper ions. At 376 and 430 nm, the HCPyTSC exhibits selective sensing for Cu2+ and F- ions. By examining the natural bond orbital (NBO) analysis and the potential energy curve (PES) of the ground state for the function of the C-H bond, it has been determined from the theoretical study at hand that the deprotonation was taken from the 'CH' proton of the pyrazole ring. For F- and Cu2+, the HCPyTSC detection limits were 4.62 nM and 15.36 nM, respectively. Similarly, the binding constants (Kb) for F- and Cu2+ ions in acetonitrile medium were found to be 2.06 × 105 M-1 and 1.88 × 105 M-1. Chemosensor HCPyTSC with and without F- and Cu2+ ions have an emission and absorption response that can imitate a variety of logic gates, including the AND, XOR, and OR gates. Additionally, a paper-based sensor strip with the HCPyTSC was created for use in practical, flexible F- sensing applications. The paper-based sensor was more effective in detecting F- than other anions. The effectiveness of HCPyTSC for the selective detection of F- in living cells as well as its cell permeability were examined using live-cell imaging in T24 cells.

Design of an anticancer organoruthenium complex as the guest and polydiacetylene-coated fluorogenic nanocarrier as the host: engineering nanocarrier using ene-yne conjugation for sustained guest release, enhanced anticancer activity and reduced in vivo toxicity.

Despite the enormous efforts made over the past two decades to develop metallodrugs and nanocarriers for metallodrug delivery, there are still few precise strategies that aim to optimize the design of both metallodrugs and metallodrug carriers jointly in a concerted effort. In this work, three half-sandwich ruthenium(II) complexes with pyridylimidazo[1,5-a]pyridine ligand functionalized with polycyclic aromatic moiety (Ru(nap), Ru(ant), Ru(pyr)) are evaluated as possible anticancer candidates and polydiacetylene (PDA)-coated amino-functionalized mesoporous silica nanoparticles (AMSNs) are designed as a functional nanocarrier for drug delivery. Ru(pyr) exhibits higher cytotoxicity in HT-29 colorectal cancer cells compared to other complexes and cis-platin, but it does not exhibit better cellular uptake. Ru(pyr) is found to be preferentially accumulated in plasma, mitochondria, and ER-Golgi membrane. The complex induces cell cycle arrest in the G0/G1 phase, while higher concentrations cause programmed cell death via apoptosis. Ru(pyr) influences cancer cell adhesion property and acts as an antioxidant in HT-29 cells. In order to modulate the anticancer potency of Ru(pyr), AMSNs are used to encapsulate the complex, and then diacetylene self-assembly is allowed to deposit on the surface of the nanoparticles. Subsequently, the nanoparticles undergo topopolymerization, which results in π-conjugated PDA-Ru(pyr)@AMSNs. Owing to the ene-yne polymeric skeleton in the backbone, the non-fluorescent AMSNs turn into red-emissive particles, which are exploited for cell imaging applications. The release profile analysis reveals that such a π-conjugated polymer prevents the premature release of the complex from porous silica nanoparticles with the accelerated release of the complex in an acidic medium compared to physiological conditions. The PDA gatekeepers have also been proven to enhance the cellular internalization of Ru(pyr) with slow continuous release from the nanoformulation. Zebrafish embryo toxicity analysis suggests that the PDA-coated nanocarriers could be suitable candidates for in vivo investigations.

Molecules that Turn Themselves Inside-Out: Tuning in/out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH2 )n )3 P Newly Accessible by Earth-Abundant-Metal Templates.

Photolyses of trans-Fe(CO)3 (P((CH2 )n )3 P) (n=10 (a), 12 (b), 14 (c), 16 (d), 18 (e)) in the presence of PMe3 provide the first economical and scalable route to macrobicyclic dibridgehead diphosphines P((CH2 )n )3 P (1). These are isolated as mixtures of in,in/out,out isomers that equilibrate with degenerate in,out/out,in isomers at 150 °C via pyramidal inversion at phosphorus. For the entire series, VT 31 P NMR data establish or bound Keq , rates, and activation parameters for a variety of phenomena, many of which involve homeomorphic isomerizations, topological processes by which certain molecules can turn themselves inside out (e. g., in,in⇌out,out). This provides the first detailed mapping of such trends in homologous series of aliphatic bicyclic compounds XE((CH2 )n )3 EX with any type of bridgehead. Isomeric diborane adducts 1 a,d ⋅ 2BH3 are also characterized. Crystal structures of out,out-1 a and in,in-1 a ⋅ 2BH3 aid isomer assignments and reveal unusual cage conformations.

Efficient ternary WORM memory devices from quinoline-based D-A systems by varying the redox behavior of ferrocene.

The design and synthesis of ferrocene-functionalized organic small molecules using quinoline cores are rendered to achieve a ternary write-once-read-many (WORM) memory device. Introducing an electron-withdrawing group into the ferrocene system changes the compounds' photophysical, electrochemical, and memory behavior. The compounds were synthesized with and without an acetylene bridge between the ferrocene unit and quinoline. The electrochemical studies proved the oxidation behavior with a slightly less intense reduction peak of the ferrocene unit, demonstrating that quinolines have more reducing properties than ferrocene with bandgaps ranging from 2.67-2.75 eV. The single crystal analysis of the compounds also revealed good interactive interactions, ensuring good molecular packing. This further leads to a ternary WORM memory with oxidation of the ferrocene units and charge transfer in the compounds. The devices exhibit on/off ratios of 104 and very low threshold voltages of -0.58/-1.02 V with stabilities of 103 s and 100 cycles of all the states through retention and endurance tests.

Mono and Dinuclear Palladium Pincer Complexes of NNSe Ligand as a Catalyst for Decarboxylative Direct C-H Heteroarylation of (Hetero)arenes.

This report describes the synthesis of a new NNSe pincer ligand and its mono- and dinuclear palladium(II) pincer complexes. In the absence of a base, a dinuclear palladium pincer complex (C1) was isolated, while in the presence of Et3 N base a mononuclear palladium pincer complex (C2) was obtained. The new ligand and complexes were characterized using techniques like 1 H, 13 C{1 H} nuclear magnetic resonance (NMR), fourier transform infrared (FTIR), high-resolution mass spectrometry (HRMS), ultraviolet-visible (UV-Visible), and cyclic voltammetry. Both the complexes showed pincer coordination mode with a distorted square planar geometry. The complex C1 has two pincer ligands attached through a Pd-Pd bond in a dinuclear pincer fashion. The air and moisture-insensitive, thermally robust palladium pincer complexes were used as the catalyst for decarboxylative direct C-H heteroarylation of (hetero)arenes. Among the complexes, dinuclear pincer complex C1 showed better catalytic activity. A variety of (hetero)arenes were successfully activated (43-87 % yield) using only 2.5 mol % of catalyst loading under mild reaction conditions. The PPh3 and Hg poisoning experiments suggested a homogeneous nature of catalysis. A plausible reaction pathway was proposed for the dinuclear palladium pincer complex catalyzed decarboxylative C-H bond activation reaction of (hetero)arenes.

Rapid Assembly of Functionalized 2H-Chromenes and 1,2-Dihydroquinolines via Microwave-Assisted Secondary Amine-Catalyzed Cascade Annulation of 2-O/N-Propargylarylaldehydes with 2,6-Dialkylphenols.

An efficient, secondary amine-catalyzed cascade annulation of 2-O/N-propargylarylaldehydes with 2,6-dialkylphenols was established to access biologically relevant functionalized 2H-chromenes and 1,2-dihydroquinolines tethered with a synthetically useful p-quinone methide scaffold in high yields under microwave irradiation and conventional heating conditions. The microwave-assisted strategy was convenient, clean, rapid, and high yielding in which the reactions were completed in just 15 min, and the yields obtained were up to 95%. This highly atom-economical domino process constructed two new C-C double bonds and a six-membered O/N-heterocyclic ring in a single synthetic operation. Its mechanism process was rationalized as involving sequential iminium ion formation, nucleophilic addition, and intramolecular annulation steps. Furthermore, the synthesized 2H-chromene derivatives were transformed into valuable indeno[2,1-c]chromenes, 5H-indeno[2,1-c]quinolines, and oxireno[2,3-c]chromene via a palladium-catalyzed double C-H bond activation process and epoxidation, respectively.

Development of Nonclassical Photoprecursors for Rh2 Nitrenes.

Characterization of reactive intermediates in C-H functionalization is challenging due to the fleeting lifetimes of these species. Synthetic photochemistry provides a strategy to generate post-turnover-limiting-step intermediates in catalysis under cryogenic conditions that enable characterization. We have a long-standing interest in the structure and reactivity of Rh2 nitrene intermediates, which are implicated as transient intermediates in Rh2-catalyzed C-H amination. Previously, we demonstrated that Rh2 complexes bearing organic azide ligands can serve as solid-state and in crystallo photoprecursors in the synthesis of transient Rh2 nitrenoids. Complementary solution-phase experiments have not been available due to the weak binding of most organic azides to Rh2 complexes. Furthermore, the volatility of the N2 that is evolved during in crystallo nitrene synthesis from these precursors has prevented the in crystallo observation of C-H functionalization from lattice-confined nitrenes. Motivated by these challenges, here we describe the synthesis and photochemistry of nonclassical nitrene precursors based on sulfilimine ligands. Sulfilimines bind to Rh2 carboxylate complexes more tightly than the corresponding azides, which has enabled the full solid-state and solution-phase characterization of these new complexes. The higher binding affinity of sulfilimine ligands as compared with organic azides has enabled both solution-phase and solid-state nitrene photochemistry. Cryogenic photochemical studies of Rh2 sulfilimine complexes confined within polystyrene thin films demonstrate that sulfilimine photochemistry can be accomplished at low temperature but that C-H amination is rapid at temperatures compatible with N═S photoactivation. The potential of these structures to serve as platforms for multistep in crystallo cascades is discussed.

1-Benzyl-3-[(4-meth-oxy-phen-yl)imino]-indolin-2-one.

The title compound, C22H18N2O2, is a Schiff base obtained by condensing p-arnisidine (4-meth-oxy-aniline) with N-benzyl-isatin (1-benzyl-1H-indole-2,3-dione), which crystallizes in the triclinic P space group. The benzyl and phenyl rings subtend dihedral angles of 76.08 (7) and 60.70 (6)°, respectively, with the isatin group. The imino C=N double bond exists in an E conformation.

Spin diffusion in the Phosphorus-31 NMR relaxation in a layered crystalline α-Sn(IV) phosphate contaminated by paramagnetic impurities.

The study of a layered crystalline Sn(IV) phosphate by solid-state NMR has demonstrated that the 31P T1 relaxation of phosphate groups, dependent on spinning rate is completely controlled by the limited spin diffusion to paramagnetic ions found by EPR. The spin-diffusion constant, D(SD), was estimated as 2.04 10-14 cm2s-1. The conclusion was supported by the 31P T1 time measurements in zirconium phosphate 1-1, also showing paramagnetic ions and in diamagnetic compound (NH4)2HPO4.

Diversity-Oriented Synthesis of Benzo[f][1,4]oxazepine-, 2H-Chromene-, and 1,2-Dihydroquinoline-Fused Polycyclic Nitrogen Heterocycles under Microwave-Assisted Conditions.

An efficient, diversity-oriented synthesis of oxazepino[5,4-b]quinazolin-9-ones, 6H-chromeno[4,3-b]quinolines, and dibenzo[b,h][1,6]naphthyridines was established involving a substrate-based approach under microwave-assisted and conventional heating conditions in high yields (up to 88%). The CuBr2-catalyzed, chemoselective cascade annulation of O-propargylated 2-hydroxybenzaldehydes and 2-aminobenzamides delivered oxazepino[5,4-b]quinazolin-9-ones involving a 6-exo-trig cyclization-air oxidation-1,3-proton shift-7-exo-dig cyclization sequence. This one-pot process showed excellent atom economy (-H2O) and constructed two new heterocyclic rings (six- and seven-membered) and three new C-N bonds in a single synthetic operation. On the other side of diversification, the reaction between O/N-propargylated 2-hydroxy/aminobenzaldehydes and 2-aminobenzyl alcohols delivered 6H-chromeno[4,3-b]quinolines and dibenzo[b,h][1,6]naphthyridines involving sequential imine formation-[4 + 2] hetero-Diels-Alder reaction-aromatization steps. The influence of microwave assistance was superior to conventional heating, where the reactions were clean, rapid, and completed in 15 min, and the conventional heating required a longer reaction time at a relatively elevated temperature.

Palladium-catalyzed intramolecular oxypalladation-initiated cascade: solvent-dependent chemodivergent approach to functionalized benzazepines and tetrahydroquinolines.

Palladium-catalyzed, solvent-dependent intramolecular oxypalladation-triggered domino sequences of internal alkynes bearing tethered nucleophilic carboxylic ester and electrophilic enone functionalities were developed for the chemodivergent synthesis of two completely distinct biologically significant complex molecules including isochromenone-fused benzazepines and isobenzofuranone-fused tetrahydroquinolines/chromanes in a single synthetic operation.

Hinged Bipodal Furoylthiourea-Based Ru(II)-Arene Complexes: Effect of (ortho, meta, or para)-Substitution on Coordination and Anticancer Activity.

We set out to design and synthesize bipodal ligands with the phenyl group as the spacer and varied the substitution on the spacer between ortho (L1), meta (L2), and para (L3). The respective ligands and complexes containing either p-cymene (PL1-PL3) or benzene (BL1-BL3) as the arene unit were synthesized and characterized successfully. The influence of the ligands due to substitution change on their coordination behavior was quite minimal; however, the differences were seen in the anticancer activity of the complexes. DFT studies revealed the structural variations between the three different substitutions, which was further confirmed by single-crystal X-ray diffraction studies. The anticancer activity of the complexes could be correlated with their rate of hydrolysis and their lipophilicity index as determined by UV-visible spectroscopy. The cell death mechanism of the active complexes was deduced to be apoptotic via staining assays, flow cytometry, and Western blot analysis.

Enhancing the Resistive Switching Behavior of WORM Memory Devices Using D-π-A Based Ester-Flanked Quinolines.

Donor-Acceptor systems are highly appreciated in the field of organic memory devices due to their efficient charge transport within the systems. In this work, we have designed and synthesized a D-π-A system constituting ester-flanked quinolines and functionalized triarylamines (TAA) through a single-step cross-coupling reaction to fabricate memory devices via Write-Once Read-Many times (WORM) non-volatile memory. Structure-property relationships are reconnoitered for these conjugated D-π-A systems through a series of UV, fluorescence, XRD, DFT, and memory characterizations. The UV and CV data show efficient charge transfer with intramolecular charge transfer occurring at 407-417 nm and a short band gap of 2.56-2.65 eV. An enhancement in the resistive switching behavior of the memory devices is observed for the compounds with simple TAA-quinoline and tert-butylphenyl substituted TAA and fluorophenyl substituted quinoline due to balanced charge distribution in the compounds. This enhanced switching induces an on/off ratio of 103 by generating a highly ordered arrangement in the thin films. The HOMO, LUMO levels, and the ESP images together estimate a charge transfer and charge trapping as the plausible mechanism for the solution-processable WORM memory devices. The longer retention time (103  s) and lower threshold voltages (-1.21--2.12 V) of the devices makes them intriguing compounds for memory applications.

Creating Solid Solutions of Metallocenes: Migration of Nickelocene into the Ferrocene Crystal Lattice in the Absence of a Solvent.

Ferrocene and nickelocene do not react with each other in solution; however, the large impact of the paramagnetic component on the ferrocene 1H NMR signal linewidth and relaxation times has been quantified. Co-crystallization of ferrocene and nickelocene at any ratio from a solvent can be explained with both pure substances crystallizing in the same space group P21/n. As a new phenomenon, when a ferrocene single crystal is exposed to polycrystalline nickelocene in the absence of a solvent, the nickelocene migrates into the ferrocene crystal lattice and a mixed crystal is formed that retains its macroscopic shape. This process has been proven visually by cutting the single crystal. Mixing polycrystalline ferrocene with polycrystalline nickelocene at different molar ratios with a mortar and pestle leads to crystalline solid solutions with the corresponding molar ratios of both components. This migration of one organometallic component into an existing crystal lattice of another at ambient temperature in the absence of a solvent has not been described previously. Paramagnetic 1H solid-state NMR spectroscopy of static and rotating samples of dry ferrocene/nickelocene mixtures at varying ratios is used to prove and quantify the mixing of both metallocenes at the molecular level. A single-crystal X-ray structure of a 50/50 mixed crystal corroborates the NMR results that nickelocene and ferrocene are randomly distributed in the lattice and that the space group P21/n is retained. All ferrocene molecules in the mixed crystal lattice show a broadening of their 1H wideline signals and residual magic-angle spinning (MAS) lines at ambient temperature. The broadening of the ferrocene signals correlates with the nickelocene content. 1H T1 relaxation time measurements for the signals of ferrocene in samples with different amounts of nickelocene corroborate the assumption that the signal broadening is due to paramagnetic dipole-dipole relaxation of ferrocene molecules in the vicinity of nickelocene. Spatially separated ferrocene and nickelocene powders in one rotor show the solid-state NMR characteristics of the individual polycrystalline metallocenes. The described formation of solid solutions of metallocenes in the absence of a solvent will open new pathways to homogeneously mixed nanoparticles with desired metal ratios and dual-atom catalysts.

Building Blocks for Molecular Polygons Based on Platinum Vertices and Polyynediyl Edges.

Reactions of Cl2P(CH2)3PCl2 and p-MgBrC6H4X (X = a/OMe, b/OtBu, c/tBu, d/SiMe3) give the diphosphines (p-XC6H4)2P(CH2)3P(p-C6H4X)2 (1a-d; 47-66%). Additions of 1a,d to (COD)PtCl2 yield (CH2(CH2P(p-C6H4X)2)2)PtCl2 (2a,d; 62-88%), which upon reaction with butadiyne (2 equiv; HNEt2/cat. CuI) give (CH2(CH2P(p-C6H4X)2)2)Pt((C≡C)2H)2 (3a,d; 34-76%). Alternatively, 3a-d can be accessed from trans-(p-tol3P)2Pt((C≡C)2H)2 and 1a-d (30-87%). Reactions of (p-tol3P)2PtCl2 and H(C≡C)2SiR3 (2 equiv, HNEt2/cat. CuI; R = Me/Et/iPr) give trans-(p-tol3P)2Pt((C≡C)2SiR3)2 (77-95%), and subsequent additions of 1a,b,d yield the corresponding adducts (CH2(CH2P(p-C6H4X)2)2)Pt((C≡C)2SiR3)2 (R/X = Me/OMe, 5a; iPr/OMe, 6a; iPr/OtBu, 6b; iPr/SiMe3, 6d; 52-95%) and (for 5a) a luminescent diplatinum byproduct with trans Pt((C≡C)2SiMe3)2 units. 5a and 6b hydrolyze in the presence of F- to 3a,b (92-93%). Reaction of 2a and 3a (HNEt2/cat. CuI) affords the Pt4C16 polygon ([(CH2(CH2P(p-C6H4OMe)2)2)Pt(C≡C)2]4 as an H2NEt2+ Cl- adduct (66%). The 13C{1H} NMR spectra of 3a-d, 5a, and 6a,b,d feature complex AMXX' (CPtPP') spin systems, and simulations allow J values to be extracted. The crystal structures of 2a, 3a,b,d, 5a, and 6a are determined and analyzed.

Monodisperse Molecular Models for the sp Carbon Allotrope Carbyne; Syntheses, Structures, and Properties of Diplatinum Polyynediyl Complexes with PtC20Pt to PtC52Pt Linkages.

Extended conjugated polyynes provide models for the elusive sp carbon polymer carbyne, but progress has been hampered by numerous synthetic challenges. Stabilities appear to be enhanced by bulky, electropositive transition-metal endgroups. Reactions of trans-(C6F5)(p-tol3P)2Pt(C≡C)nSiEt3 (n = 4-6, PtCxSi (x = 2n)) with n-Bu4N+F-/Me3SiCl followed by excess tetrayne H(C≡C)4SiEt3 (HC8Si) and then CuCl/TMEDA and O2 give the heterocoupling products PtCx+8Si, PtCx+16Si, and sometimes higher homologues. The PtCx+16Si species presumably arise via protodesilylation of PtCx+8Si under the reaction conditions. Chromatography allows the separation of PtC16Si, PtC24Si, and PtC32Si (from n = 4), PtC18Si and PtC26Si (n = 5), or PtC20Si and PtC28Si (n = 6). These and previously reported species are applied in similar oxidative homocouplings, affording the family of diplatinum polyynediyl complexes PtCxPt (x = 20, 24, 28, 32, 36, 40 in 96-34% yields and x = 44, 48, 52 in 22-7% yields). These are carefully characterized by 13C NMR, UV-visible, and Raman spectroscopy and other techniques, with particular attention to behavior as the Cx chain approaches the macromolecular limit and endgroup effects diminish. The crystal structures of solvates of PtC20Pt, PtC24Pt, and PtC26Si, which feature the longest sp chains structurally characterized to date, are analyzed in detail. All data support a polyyne electronic structure with a nonzero optical band gap and bond length alternation for carbyne.

Migration of Hydride, Methyl, and Chloride Ligands between Al and M in (PAlP)M Pincer Complexes (M = Rh or Ir).

Protolysis of AlMe3 or AlBui3 with 2-diisopropylphosphinopyrrole (1) yields molecules containing two flanking phosphines and a central Al-Me (2-Me), Al-iBu (2-iBu), or Al-H (2-H) unit. The reactions of 2-Me with [L2MCl]2 (L = cyclooctene or 1/2 1,5-cyclooctadiene and M = Rh or Ir) in the presence of pyridine produces PAlClP pincer complexes (3-Rh and 3-Ir) with Al-Cl and M-Me bonds. The analogous reaction of a mixture of 2-iBu and 2-H with [L2MCl]2 and pyridine resulted in the formation of analogous Rh-H (4-Rh) and Ir-H (4-Ir) complexes. Treatment of 3-Rh with NaBEt3H produced compound 5-Rh with an Al-Me and a Rh-H bond; the analogous reaction of 3-Ir did not result in a clean product. 4-Ir accepted an equivalent of H2 to produce 6-Ir with two terminal Ir-H bonds and one bridging Al-H-Ir moiety, whereas 4-Rh did not react with H2. The density functional theoretical treatment is in accord with this finding, highlights the likely mechanism for the H2 addition, and supports the bonding picture in 6-Ir arising from NMR and X-ray diffraction (XRD) observations. Spectroscopic data and XRD studies are consistent with distorted square-pyramidal structures (about Rh or Ir) for compounds 3-5, with an alane occupying the apical position. Complexes 3 and 4 possess some of the shortest known Rh-Al or Ir-Al distances.