The condensation reaction of resorcinol with cis-[ClP(μ-N(t)Bu)(2)PN(H)(t)Bu] produced a difunctional derivative 1,3-C(6)H(4)[OP(μ-N(t)Bu)(2)PN(H)(t)Bu](2) (1), whereas the similar reaction with [ClP(μ-N(t)Bu)](2) resulted in the formation of a 1:1 mixture of dimeric and tetrameric species, [{P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](2) (2a) and [{P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](4) (2b), which were separated by repeated fractional crystallization and column chromatography. The reaction of dimer 2a with H(2)O(2) and selenium produces tetrachalcogenides [{(O)P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](2) (3) and [{(Se)P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](2) (4), respectively. The reaction between the dimer (2a) and [Pd(μ-Cl)(η(3)-C(3)H(5))](2) or AuCl(SMe(2)) yielded the corresponding tetranuclear complexes, [{((Cl)(η(3)-C(3)H(5))Pd)P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](2) (5) and [{(ClAu)P(μ-N(t)Bu)}(2){1,3-(O)(2)-C(6)H(4)}](2) (6) in good yield. The complexes 5 and 6 are the rare examples of phosphorus macrocycles containing two or more exocyclic transition metal fragments. Treatment of 1 with copper halides in 1:1 molar ratio resulted in the formation of one-dimensional (1D) coordination polymers, [(CuX){1,3-C(6)H(4){OP(μ-N(t)Bu)(2)PN(H)(t)Bu}}(2)](n) (7, X = Cl; 8, X = Br; 9, X = I), which showed the helical structure in solid state because of intramolecular hydrogen bonding, whereas similar reactions of 1 with 4 equiv of copper halides also produced 1D-coordination polymers, [(Cu(2)X(2))(2){1,3-C(6)H(4){OP(μ-N(t)Bu)(2)PN(H)(t)Bu}(2)}](n) (10, X = Cl; 11, X = Br; 12, X = I), but containing Cu(2)X(2) rhomboids instead of CuX linkers. The crystal structures of 1, 2a, 2b, 4, 7-9, and 12 were established by X-ray diffraction studies.

The triazine-based trisphosphine, 2,4,6-tris(diphenylphosphino)-1,3,5-triazine (1) was prepared in improved yield by reacting cyanuric chloride with 3 equiv of trimethylsilyldiphenylphosphine. The solid-state structure of 1 showed short intermolecular P···P contacts of 3.362 Å, which is significantly shorter than the sum of the van der Waals radii of phosphorus atoms (3.6 Å). The reaction of 2,4,6-tris(diphenylphosphino)-1,3,5-triazine (1) with copper(I) salts in a 2:3 molar ratio yielded various cyclophane-type complexes in quantitative yield. The solid-state structures of these clusters have been found to depend on the size of the halide ions, the solvent employed, and the reaction conditions. Copper(I) chloride formed a monomeric metallocyclophane, whereas copper(I) bromide and copper(I) iodide derivatives preferred dimeric and 1D-polymeric structures, respectively. The tricationic complexes derived from Cu(I) ion and 2,4,6-tris(diphenylphosphino)-1,3,5-triazine also adopted monomeric metallocyclophane structures. These complexes have been employed in the A(3) coupling reaction under microwave irradiation. The copper(I) iodide derivative showed excellent catalytic efficiency.

Acyl phosphines (R2P–C(O)R) are the tertiary phosphorus compounds having a P–C(O) linkages. Though they are known historically, their literature is not exhaustive mainly due to the vulnerability of P–C(O) bonds toward nucleophilic substitution reactions. However, there is a renewed interest in the synthesis of acyl phosphines and di (acyl) phosphines, recently. Among the methods available for the synthesis, most involve nucleophilic substitutions at carbonyl carbon by phosphorus nucleophile as a customary step. The examples of phosphines possessing two acyl groups (R(O)C–RP–C(O)R) are found more frequently in the literature of late, and most of them are cyclic in nature. The transition‐metal complexes of acyl phosphines and di (acyl) phosphines are moderately explored in literature. However, their catalytic applications are meager. In the current review, the details of syntheses, reactivity, structural features, and catalytic activities of acyl phosphines and bis (acyl) phosphines reported in the last three decades are discussed.

This paper describes the syntheses of two novel cyclodiphosphazane derivatives and their coordination chemistry with CuI, RuII, RhI, PdII and AuI is also described.

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A new heterogeneous catalyst was synthesized by immobilizing Pd on areca nut kernel‐derived carbon nanospheres (CNSs). The CNSs, without any further activation processes, accommodated 3% of Pd on their surface. The new Pd/CNS material was used for the reduction of nitroarenes and Suzuki–Miyaura coupling of bromoarenes with aryl boronic acids. The reactions were conducted under microwave irradiation at 160 °C using 12 mol% of Pd/CNS (0.36% actual Pd content). The reduction of nitroarenes into their respective amino compounds was achieved in 10–20 min (conversion up to 100%); by contrast, the Suzuki–Miyaura reactions yielded up to 98% at 150 °C with 10 mol% of Pd/CNS catalyst. The products were identified using gas chromatography and nuclear magnetic resonance spectroscopy. The catalyst was isolated from reaction mixture and reused without any significant loss in the activity. Thus, the present work introduces one‐pot‐derived porous CNSs as efficient catalytic support to Pd, establishing an alternative to existing Pd/C in terms of cost and efficiency.

The copper(i) complexes containing phosphorus donor ligands such as diazadiphosphetidine, cis-{(o-OCH2C5H4N)P(μ-N(t)Bu)}2 (1) and aminobis(phosphonite), C6H5N{P(OC6H3(OMe-o)(C3H5-p))2}2 (2, PNP), have been synthesized. Treatment of 1 with copper iodide afforded the 1D coordination polymer [{Cu(μ-I)}2{(o-OCH2C5H4N)P(μ-N(t)Bu)}2]n (3). Treatment of 3 with 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) produced mixed-ligand complexes [(L)2Cu2{(o-OCH2C5H4N)P(μ-N(t)Bu)}2][I]2 (4 L = bpy; 5 L = phen) in good yields. The reaction of 2 with copper iodide yielded a rare tetranuclear copper complex [(CuI)2C6H5N(PR2)2]2 (6), which on subsequent treatment with various pyridyl ligands produced binuclear complexes [{Cu(μ-I)(py)}2(μ-PNP)] (7), [Cu2(μ-I)(bpy)2(μ-PNP)]I (8), [Cu2(μ-I)I(bpy)(μ-PNP)] (9), [Cu2(phen)(bpy)(μ-PNP)](OTf)2 (10), [Cu2(μ-I)I(phen)(μ-PNP)] (11) and [Cu2(μ-I)(phen)2(μ-PNP)]I (12), in an almost quantitative yield. The new copper(i) complexes (4, 5 and 7-12) were tested for anti-cancer activity against three human tumor cell lines. Compounds 5, 10 and 12 showed in vitro antitumor activity 5-7 fold higher than cisplatin, the most used anticancer drug. These three most potent compounds (5, 10 and 12) were chosen for detailed study to understand their mechanism of action. The copper(i) compounds studied in the present investigation were found to inhibit tumor cell growth by arresting cells at the S-phase of the cell cycle. The characteristic nuclear morphology of treated cells showed signs of DNA damage. The experimental evidence clearly indicated that these compounds initiated apoptosis, which is mediated through the p53 pathway.

This paper describes the synthesis of resorcin[4]arene based octaphosphinite ligands and their tetra-pincer NiII and PdII complexes and rhodium-octaphosphinite catalyzed hydroformylation of styrene and its derivatives.