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Cyclodiphosphazanes containing phosphine or phosphine plus amide functionalities {(tBuNP(OC6H4PPh2-o)}2(3), {tBuNP(OCH2CH2PPh2)}2(4), {tBuHN(tBuNP)2OC6H4PPh2-o} (5), and {tBuHN(tBuNP)2OCH2CH2PPh2} (6) were synthesized by reacting cis-{tBuNPCl}2(1) and cis-[tBuHN(tBuNP)2Cl] (2) with corresponding phosphine substituted nucleophiles. The reactions of 3and 5with excess of elemental sulfur or selenium produce the corresponding tetra and trichalcogenides, {(tBuNP(E)(OC6H4P(E)Ph2-o)}2(7, E = S; 8, E = Se) and {tBuHN(tBuNP)2OC6H4P(E)Ph2-o} (9, E = S; 10, E = Se), respectively, in quantitative yields. The reactions between 3and [Rh(COD)Cl]2or [M(COD)Cl]2(M = Pd or Pt) afford bischelated complexes [Rh(CO)Cl{tBuNP(OC6H4PPh2-o)}]2(11), and [MCl2{tBuNP(OC6H4PPh2-o)}]2(12, M = Pd; 13, M = Pt) in good yield. The 1 : 2 reaction between 3and [PdCl(η3-C3H5)]2in dichloromethane resulted initially in the formation of a tripalladium complex of the type [Pd3Cl4(η3-C3H5)2{tBuNPOC6H4PPh2}2] (14a) which readily reacts with moisture to form an interesting binuclear complex, [Cl2Pd{μ-(PPh2C6H4OP(μ-tBuN)2P(O)}(μ-Cl)Pd(OC6H4PPh2)] (14b). One of the palladium(ii) atoms forms a simple six-membered chelate ring, whereas the other palladium(ii) atom facilitates the moisture assisted cleavage of one of the endocyclic P–O bonds followed by the oxidation of P(iii) to P(v) thus forming a Pd–P σ-bond. The broken ortho-phosphine substituted phenoxide ion forms a five-membered palladacycle with the same palladium(ii) atom. Similar reaction of 5with [PdCl(η3-C3H5)]2also affords a binuclear complex [{PdCl(η3-C3H5)}tBuNH{tBuNP}2OC6H4PPh2{PdCl2}] (15) containing a PdCl2moiety which forms a six-membered chelate ring viaring-phosphorus and PPh2moieties on one side and a PdCl(η3-C3H5) fragment coordinating to amide bound phosphorus atom on the other side of the ring. Treatment of 3with four equivalents of AuCl(SMe2) produces a tetranuclear complex, [(AuCl)4{tBuNP(OC6H4PPh2)}2] (16), whereas a 1 : 3 reaction between 5and AuCl(SMe2) leads to the formation of a trinuclear complex, [tBuNH{tBuNP(AuCl)}2OC6H4P(AuCl)Ph2] (17). The crystal structures of 3, 5, 9–11and 13–17are reported. [ABSTRACT FROM AUTHOR]

Reactions of two equivalents of [AuCl(SMe2)] with cyclodiphosphazanes cis-{RP(μ-NtBu)}2(1a–1d) produce binuclear gold(i) complexes of the type, [ClAu{RP(μ-NtBu)}2AuCl] (2R = OC6H4OMe-o, 3R = OCH2CH2OMe, 4R = NEt2, 5R = NHtBu) in quantitative yield. A similar reaction between cis-{(o-MeOC6H4O)P(μ-NtBu)}2(1a) and [AuCl(SMe2)] in a 1 : 1 molar ratio afforded the mono-nuclear complex [ClAu{(o-MeOC6H4O)P(μ-NtBu)}2] (6). Addition of two equivalents of CuX (X = Br, I) to the chloro derivative 2leads to the formation of bromo, [BrAu{(o-MeOC6H4O)P(μ-NtBu)}2AuBr] (7), and iodo, [IAu{(o-MeOC6H4O)P(μ-NtBu)}2AuI] (8), derivatives through halogen exchange reactions. A tetranuclear gold(i) macrocycle [Au{(o-MeOC6H4O)P(μ-NtBu)}2]4(ClO4)4(9) and a mononuclear gold(i) complex [Au({(o-MeOC6H4O)P(μ-NtBu)}2)2]ClO4(10) were obtained, respectively, from 1 : 1 and 2 : 1 stoichiometric reactions between 1aand [Au(SMe2)2]ClO4. Molecular structures of complexes 4, 6, 7, 8and 9are confirmed by single-crystal X-ray diffraction studies. Interestingly, the crystal structure of the tetra-nuclear AuImacrocycle 9reveals the encapsulation of one ClO4−anion inside the bowl shaped macrocyclic cavity through weak AuO and C–HO interactions. [ABSTRACT FROM AUTHOR]

The reactions of phenylene-1,4-diaminotetra(phosphonite), p-C6H4[N{P(OC6H4OMe-o)2}2]2(P2N(Ph)NP2) (1) with [Rh(COD)Cl]2in 1 : 2 and 1 : 1 molar ratio produce tetra- and polymetallic chelate complexes, [Rh4(COD)2(μ-Cl)4(P2N(Ph)NP2)] (2) and [Rh2(μ-Cl)2(P2N(Ph)NP2)]n(3), respectively. Similar reaction of 1with [Rh(COD)Cl]2in dichloromethane–acetonitrile mixture furnishes a dinuclear complex, [Rh2Cl2(CH3CN)2(P2N(Ph)NP2)] (4). The reaction of 3or 4with CO affords a dinuclear carbonyl derivative, [Rh2Cl2(CO)2(P2N(Ph)NP2)] (5). Treatment of 4with 2 equivalents of pyrazine or 4,4′-bipyridine produce one-dimensional RhIcoordination polymers, [Rh2Cl2(C4H4N2)(P2N(Ph)NP2)]n(6) and [Rh2Cl2(C10H8N2)(P2N(Ph)NP2)]n(7) in quantitative yields. The catalytic activity of RhIcomplexes 2–7have been investigated in transfer hydrogenation reactions. [ABSTRACT FROM AUTHOR]

The large-bite bis(phosphite) ligand [{(–OC10H6(μ-S)C10H6O–)P{μ-(–OC10H6(μ-S)C10H6O–)}P(–OC10H6(μ-S)C10H6O–)}] (P⁁P) (2) was obtained by the reaction of PCl3 and thiobis(2,2′-naphthol) (1). The stoichiometric reactions of 2 with elemental sulfur and selenium afforded the corresponding chalcogenide derivatives [(E)P⁁P(E)] (3, E = S; 4, E = Se) in good yield. Treatment of two equivalents of [ClAu(SMe2)] with 2 afforded a dinuclear complex [ClAu(P⁁P)AuCl] (5), whereas the 1 : 1 reaction with CuI yielded the [(P⁁P)CuI] (6) complex. The copper(i) complex 6 on treatment with various pyridyl derivatives, produced mixed-ligand complexes [(P⁁P)CuI(NC5H5)] (7), [(P⁁P)Cu(2,2′-bpy)]I (8), [(P⁁P)Cu(1,10-phen)]I (9) and {[(P⁁P)Cu(4,4′-bpy)]I}∞ (10). The compounds 2–5 were tested for their cytotoxic activity on the human cervical cancer (HeLa) cell line. Compounds 2 and 3 were found to inhibit proliferation of HeLa cells significantly. These agents also induced apoptotic cell death in cancer cells. Evidence presented in this study indicated that the compounds 2 and 3 activate the tumor suppressor protein p53 in the colon adenocarcinoma (HCT-116) cell line. [ABSTRACT FROM AUTHOR]

The 1 : 1 reaction between the cyclodiphosphazane cis-{(o-MeOC6H4O)P(µ-NtBu)}2 (1) and AgOTf afforded one-dimensional AgI coordination polymer [Ag{µ-OTf-κO,κO}{µ-(o-MeOC6H4O)P(µ-NtBu)-κP,κP}2]∞ (2) containing bridging cyclodiphosphazane and trifluoromethanesulfonate (OTf) ligands. The 2 : 1 reaction of 1 and AgOTf leads to the formation of simple mononuclear complex [Ag{OTf-κO,κO}({(o-MeOC6H4O)P(µ-NtBu)-κP}2)2] (3) in quantitative yield. Reaction of 1 with AgCN produces a strain-free zig-zag coordination polymer [({(o-MeOC6H4O)P(µ-NtBu)-κP,κP}2)2Ag(NCAgCN)]∞ (4) irrespective of reaction stoichiometry and conditions. In complexes 3 and 4 cyclodiphosphazanes coordinate to AgI centers in a monodentate fashion. Single crystal structures were established for the AgI polymers 2 and 4. [ABSTRACT FROM AUTHOR]

Novel octanuclear copper(i) macrocyclic complexes and hexanuclear 2-dimensional grid-like polymers containing [P(μ-NR)]2 scaffold in which the anionic moieties are trapped inside the cationic macrocyclic cavities are reported. [ABSTRACT FROM AUTHOR]

Novel octanuclear copper(i) macrocyclic complexes and hexanuclear 2-dimensional grid-like polymers containing [P(μ-NR)]2 scaffold in which the anionic moieties are trapped inside the cationic macrocyclic cavities are reported. [ABSTRACT FROM AUTHOR]

Ureido pyrimidinedione derivatives with phenyl, 1-naphthyl and 2-naphthyl substituents form stable dimers via quadruple hydrogen bonding, but the 1-naphthyl derivative presents an unexpected tautomer in the solid state. [ABSTRACT FROM AUTHOR]