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Azomethine based substances containing triphenylamine and aminoflourene core, (E)-N-(4-(diphenylamino)benzylidene)-9H-fluorene-2-amine ((C18H14N)CH N(C13H9)) (C1), (E)-N-(4,4’-9H-fluorene-2-amine)phenyl)-N-phenylbenzeneamine ((C13H9)N CH(C18H13N)CH N(C13H9)) (C2) have been synthesized for the application in solar cells as hole transport materials. The structure of the compounds C1 and C2 has been confirmed by using FTIR, Mass, 1H NMR, 13C NMR spectroscopy and elemental analysis. The optical properties of the compounds have been investigated by using UV–Visible and fluorescence spectroscopy. Bathochromic shift in the emission spectrum of the compounds as a function of solvent polarity was studied in terms of Lippert-Mataga approximation and correlated with theoretical studies. The experimentally observed HOMO and LUMO levels of both compounds were corroborated with the theoretically calculated values which were found to be comparable with the values of existing hole transport materials.

Background: Mitochondria are prone to oxidative stress induced by chemicals and resulting in cardiac damage which can be ameliorated by the use of herbal drugs. Zanthoxylum armatum (Z. armatum) fruit are used as age-old herbal remedies. Their pharmacological and therapeutics actions are not exploited in detail. Objective: The present study is to analyze the antioxidants in the heart mitochondria of the rats challenged with isoproterenol hydrochloride (ISO) and the ameliorative effect of Z. armatum fruit. Method: The antioxidant effect of hydroethanolic extract of Z. armatum fruit on mitochondrial dysfunction induced by ISO in rats were appraised by studying the antioxidant enzymes namely superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px) and glutathione S-transferase (GST) and lipid peroxidation (LPO) in mitochondrial fractions. Results: Pretreatment with Z. armatum fruit at two different concentrations (200mg, 400mg/kg body weight) not only increased the activities of endogenous antioxidant enzymes (SOD, CAT, GPx, GST) and reduced glutathione (GSH) but also decreased the level of LPO in myocardial infarction (MI) induced rat heart mitochondria exposed to ISO. Conclusion: The enhanced antioxidant activity of Z. armatum fruit protected the heart mitochondria in rats against ISO-induced damage. This study may have a significant impact on the diseases that is caused by free radicals and the role of antioxidants in averting the diseases.

Acyclic bis(cyclodiphosphazane) [(t)BuHN((t)BuNP)(2)OCH(2)](2) (2) containing alkoxo and amido functionalities was synthesized by reacting cis-[(t)BuHN((t)BuNP)(2)Cl] (1) with ethylene glycol and upon further treatment with 4 equiv of elemental sulfur or selenium affords the corresponding tetrachalcogenides [(t)BuHN((t)BuNPE)(2)OCH(2)](2) (3, E = S; 4, E = Se) in quantitative yield. The reaction of 2 with 2 equiv of elemental sulfur results in the oxidation of only the amido-phosphorus atoms to form the di(sulfide) derivative [(t)BuHN(S)P(mu-(t)BuN)POCH(2)](2) (5). The reaction of 2 with 2 equiv of [PdCl(eta(3)-C(3)H(5))](2) afforded the tetrametallic complex [{Pd(eta(3)-allyl)Cl}(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (7) containing four independent [PdCl(2)(eta(3)-C(3)H(5))] moieties each coordinated to a phosphorus atom. In contrast, the reaction between [Pd(PEt(3))Cl(2)](2) and 2 leads to the addition of two metal atoms with the formation of [{Pd(PEt(3))Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (8), in which alternating phosphorus atoms of the bis(cyclodiphosphazane) are coordinated to palladium. Interestingly, the palladium(II) atom coordinated to the phosphorus atom bearing the t-butylamino substituent adopts a trans geometry, whereas that coordinated to the phosphorus atom connected to the -OCH(2)CH(2)O- linker prefers a cis conformation. The reaction between 2 and [Rh(COD)Cl](2) produces exclusively the bimetallic complex [{Rh(COD)Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (6) irrespective of the stoichiometry of the reactants and the reaction conditions. In complex 6, only the alkoxo-phosphorus atoms are coordinated. However, complex 6 upon treatment with AuCl(SMe(2)) in a 1:2 ratio gives the heterometallic tetrasubstituted complex [{Rh(COD)Cl}(2)(AuCl)(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (10). The reaction between 4 equiv of AuCl(SMe(2)) and 2 resulted in the formation of a tetrametallic gold complex [(AuCl)(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (9). The crystal structures of 2-4 and 7-10 are reported.

The mononuclear rhodium complexes of cyclodiphosphazane [(cod)RhCl{L-κP}] (1a) (L = cis-{(o-MeOC6H4O)P(μ-NtBu)}2) and trans-[Rh(CO)Cl{L-κP}2] (1b) react in a 1:1 molar ratio with [AuCl(SMe2)] to form the heteronuclear complexes [(cod)RhCl{μ-L-κP,κP}AuCl] (2) and trans-[Rh(CO)Cl{μ-L-κP,κP}2(AuCl)2] (7), respectively, in quantitative yield. The reaction between 1a and CuCl afforded a tetranuclear complex [(cod)RhCl{μ-L-κP,κP}Cu(μ-Cl)]2 (3). Under similar reaction conditions 1 reacts with 2 equiv. of CuX (X = Br, I) to produce the heteronuclear complexes [(cod)RhBr{μ-L-κP,κP}Cu(μ-Br)]2 (4) and [((cod)RhI{μ-L-κP,κP})2Cu(μ-X)2Cu] (X ≈ 1:1 mixture of Cl and I disordered over both sites) (5), respectively, in which two molecules of 1a are bridged by the rhombic, disordered, mixed halide [Cu(μ-X)2Cu] (5: X = Br; 6: X = Cl, I) unit. The crystal structures of 4 and 5 confirm the halogen exchange between the Rh–Cl and CuX (X = Br, I) moieties which leads to the formation of Rh–Br and Rh–I bonds. The heterodinuclear RhI/PdII complex [(cod)RhCl{μ-L-κP,κP}PdCl(η3-C3H5)] (6) was synthesized by the reaction of 1a with [PdCl(η3-C3H5)]2 in a 2:1 ratio. Reaction of 1b with CuI leads to the formation of the tetranuclear complex [Rh(CO)I{μ-L-κP,κP}2Cu(μ-I)]2 (8) containing two terminal uncoordinated phosphorus(III) centers irrespective of reactant ratio and reaction conditions. Halogen exchange reaction which leads to the formation of the Rh–I bond was also observed during the preparation of complex 8. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The tricoordinated cationic Cu-I complex [Cu(kappa(2)-P,P'-DPEphos)(kappa(1)-P-DPEphos)][BF4] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl) ether) containing a dangling phosphorus center was synthesized from the reaction of [Cu(CH3CN)(4)][BF4] with DPEphos in a 1:2 molar ratio in dichloromethane. When complex 1 is treated with MnO2, elemental sulfur, or selenium, the uncoordinated phosphorus atom undergoes oxidation to form a PE bond resulting in the formation of complexes of the type [Cu(kappa(2)-P,P'-DPEphos)(kappa(2)-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu-E bond. The zigzag polymeric Cu-I complex [Cu(kappa(2)-P,P'-DPEphos)(mu-4,4'-bpy)](n)[BF4](n) (5) was prepared by the reaction of [Cu(CH3CN)(4)][BF4] with DPEphos and 4,4'-bipyridine in an equimolar ratio. The stereochemical influences of DPEphos on its coordination behavior are examined by density functional theory calculations.

Cyclodiphosphazanes having donor functionalities such as cis-[tBuNP(OR)]2 (R = C6H4OMe-o (2); R = CH2CH2OMe (3); R = CH2CH2SMe (4); R = CH2CH2NMe2 (5)) were obtained in good yield by reacting cis-[tBuNPCl]2 (1) with corresponding nucleophiles. The reactions of 2–5 with [RuCl2(η6-cymene)]2, [MCl(COD)]2 (M = Rh, Ir), [PdCl2(PEt3)]2 and [MCl2(COD)] (M=Pd, Pt) result in the formation of exclusively monocoordinated mononuclear complexes of the type cis-[{tBuNP(OR)}2MLn-κP] irrespective of the reaction stoichiometry and the reaction conditions. In contrast, 2–5 react with [RhCl(CO)2]2, [PdCl(η3-C3H5)]2, CuX (X=Cl, Br, I) to give homobinuclear complexes. Interestingly, CuX produces both mono and binuclear complexes depending on the stoichiometry of the reactants and the reaction conditions. The mononuclear complexes on treatment with appropriate metal reagents furnish heterometallic complexes., © Elsevier

The iminophosphorane-phosphane ligand Ph 2 PC 6 H 4 OC 6 H 4 -PPh 2 =NP(O)(OPh) 2 (1) has been synthesized by partial imination of bis[2-(diphenylphosphanyl)phenyl] ether (DPEphos) with phosphoryl azide (PhD) 2 P(O)N 3 . A similar reaction in a 1:2 stoichiometry affords the bis(iminophosphorane) O-{C 6 H 4 PPh 2 =NP (O )(OPh)2)2 (2). The chalcogen derivatives O{C 6 H 4 P(E)Ph 2 } 2 [E = S (3) and Se (4)] and Ph 2 P(E)-C 6 H 4 OC 6 H 4 PPh 2 =NP (O )(OPh)2 [E = S (5) and Se (6)] are also synthesized by treating DPEphos and 1 with elemental sulfur and selenium, respectively. The mononuclear complexes trans - [MCl 2 {κ 1 -P-Ph 2 PC 6 H 4 ΟC 6 H 4 PPh 2 =NP(Ο)(OPh ) 2 } 2 ] [M = Pt (7) Pd (8)] and trans -[Rh(CO)Cl(κ 1 -P -Ph 2 PC 6 -H 4 OC 6 H 4 PPh 2 =NP (O ) (OPh ) 2 } 2 ] (12) are prepared by the reaction of 1 with [Pt(COD)Cl 2 ], [Pd(COD)Cl 2 ], and [{Rh(CO) 2 -Cl} 2 ], respectively. Treatment of 1 with [Pd 2 (dba 3 )] (dba = dibenzylideneacetone) affords the mononuclear complex [Pd 0 {κ 2 -P,O -Ph 2 PC 6 H 4 OC 6 H 4 PPh 2 =NP (O )(OPh) 2 } 2 ] (9) in which ligand 1 coordinates through its P and O centers in a κ 2 - P,O chelating fashion. The monocoordinated Au I complex [AuCl{κ 1 -P-Ph 2 PC 6 H 4 OC 6 H 4 PPh 2 =NP (O)(OPh ) 2 }] (10) has been prepared by the reaction of 1 and [AuCl(SMe 2 )] and its structure has been confirmed by X-ray crystallography. The reaction of 1 with [{Rh(COD)Cl} 2 ] in the presence of AgOTf affords the cationic Rh I complex cis-[Rh(COD)(κ 2 -P,O-Ph 2 PC 6 H 4 OC 6 H 4 PPh 2 =NP (O) (OPh) 2 }] [OTf] (11). The catalytic activity of the Pd° complex 9 has been investigated in Suzuki cross-coupling reactions. Homogeneous catalytic hydrogenation of olefins has also been studied using the cationic Rh I complex 11.

The half-sandwich complexes [(eta(5)-C5H5)RuCl(DPEphos)] (1) and [{(eta(6)-p-cymene)RuCl2}(2)(mu-DPEphos)] (2) were synthesized by the reaction of bis(2-(diphenylphosphino)phenyl) ether (DPEphos) with a mixture of ruthenium trichloride trihydrate and cyclopentadiene and with [(eta(6)-p-cymene)RuCl2](2), respectively. Treatment of DPEphos with cis-[RuCl2(dmso)(4)] afforded fac-[RuCl2(kappa(3)-P,O,P-DPEphos)(dmso)] (3). The dmso ligand in 3 can be substituted by pyridine, 2,2'-bipyridine, 4,4'-bipyridine, and PPh3 to yield trans,cis-[RuCl2(DPEphos)(C5H5N)(2)] (4), cis,cis-[RuCl2(DPEphos)(2,2'-bipyridine)] (5), trans,cis-[RuCl2(DPEphos)(mu-4,4'-bipyridine)](n) (6), and mer,trans-[RuCl2(kappa(3)-P,P,O-DPEphos)(PPh3)] (7), respectively. Refluxing [(eta(6)-p-cymene)RuCl2](2) with DPEphos in moist acetonitrile leads to the elimination of the p-cymene group and the formation of the octahedral complex cis,cis-[RuCl2(DPEphos)(H2O)(CH3CN)] (8). The structures of the complexes 1-5, 7, and 8 are confirmed by X-ray crystallography. The catalytic activity of these complexes for the hydrogenation of styrene is studied.

Acyclic bis(cyclodiphosphazane) [(t)BuHN((t)BuNP)(2)OCH(2)](2) (2) containing alkoxo and amido functionalities was synthesized by reacting cis-[(t)BuHN((t)BuNP)(2)Cl] (1) with ethylene glycol and upon further treatment with 4 equiv of elemental sulfur or selenium affords the corresponding tetrachalcogenides [(t)BuHN((t)BuNPE)(2)OCH(2)](2) (3, E = S; 4, E = Se) in quantitative yield. The reaction of 2 with 2 equiv of elemental sulfur results in the oxidation of only the amido-phosphorus atoms to form the di(sulfide) derivative [(t)BuHN(S)P(mu-(t)BuN)POCH(2)](2) (5). The reaction of 2 with 2 equiv of [PdCl(eta(3)-C(3)H(5))](2) afforded the tetrametallic complex [{Pd(eta(3)-allyl)Cl}(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (7) containing four independent [PdCl(2)(eta(3)-C(3)H(5))] moieties each coordinated to a phosphorus atom. In contrast, the reaction between [Pd(PEt(3))Cl(2)](2) and 2 leads to the addition of two metal atoms with the formation of [{Pd(PEt(3))Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (8), in which alternating phosphorus atoms of the bis(cyclodiphosphazane) are coordinated to palladium. Interestingly, the palladium(II) atom coordinated to the phosphorus atom bearing the t-butylamino substituent adopts a trans geometry, whereas that coordinated to the phosphorus atom connected to the -OCH(2)CH(2)O- linker prefers a cis conformation. The reaction between 2 and [Rh(COD)Cl](2) produces exclusively the bimetallic complex [{Rh(COD)Cl}(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (6) irrespective of the stoichiometry of the reactants and the reaction conditions. In complex 6, only the alkoxo-phosphorus atoms are coordinated. However, complex 6 upon treatment with AuCl(SMe(2)) in a 1:2 ratio gives the heterometallic tetrasubstituted complex [{Rh(COD)Cl}(2)(AuCl)(2){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (10). The reaction between 4 equiv of AuCl(SMe(2)) and 2 resulted in the formation of a tetrametallic gold complex [(AuCl)(4){(t)BuHN((t)BuNP)(2)OCH(2)}(2)] (9). The crystal structures of 2-4 and 7-10 are reported.

The reaction of [Ag(2)(k(2)-P,P'-DPEphos)(2)(mu-OTf)(2)] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl]ether) with 1,10-phenanthroline (phen) and 4,4'-bipyridine in equimolar ratios afford, respectively, the mononuclear complex [Ag(k(2)-P,P'-DPEphos)(phen)][OTf] (2) and the coordination polymer [Ag(k(2)-P,P'-DPEphos)(mu-4,4'-bpy)](n)[OTf](n) (3). In complex 3, the silver atoms are bridged by 4,4'-bipyridine units to form a zigzag metallopolymer. (c) 2008

The reaction of AgOTf in dichloromethane with bis(2-(diphenylphosphino)phenyl) ether (DPEphos) in an equimolar ratio afforded a dinuclear complex [Ag2(κ2-P,P′-DPEphos)2(μ-OTf)2] (1), whereas the similar reaction in a 1:2 molar ratio resulted in the formation of a bis-chelating complex [Ag(κ2-P,P′-DPEphos)2][OTf] (2). The silver(I) complex 1 was obtained as a dimer, in which two silver atoms are bridged by two triflate groups to form three adjacent eight-membered spirocyclic rings. The mixed-ligand complex [Ag(κ2-P,P′-DPEphos)(2,2′-bpy)][OTf] (3) was obtained in the reaction of 1 in dichloromethane with 2,2′-bipyridine. The crystal structures of complexes 1–3 were determined by single crystal X-ray analyses., © Elsevier

The title molecule, C24H16O2Si, exhibits slightly distorted tetrahedral coordination about silicon, a slight folding of each half of the molecule about the Si...O line, and π–π and C—H...π-ring interactions.

Cyclodiphosphazanes containing phosphine or phosphine plus amide functionalities {((t)BuNP(OC(6)H(4)PPh(2)-o)}(2) (3), {(t)BuNP(OCH(2)CH(2)PPh(2))}(2) (4), {(t)BuHN((t)BuNP)(2)OC(6)H(4)PPh(2)-o} (5), and {(t)BuHN((t)BuNP)(2)OCH(2)CH(2)PPh(2)} (6) were synthesized by reacting cis-{(t)BuNPCl}(2) (1) and cis-[(t)BuHN((t)BuNP)(2)Cl] (2) with corresponding phosphine substituted nucleophiles. The reactions of 3 and 5 with excess of elemental sulfur or selenium produce the corresponding tetra and trichalcogenides, {((t)BuNP(E)(OC(6)H(4)P(E)Ph(2)-o)}(2) (7, E = S; 8, E = Se) and {(t)BuHN((t)BuNP)(2)OC(6)H(4)P(E)Ph(2)-o} (9, E = S; 10, E = Se), respectively, in quantitative yields. The reactions between 3 and [Rh(COD)Cl](2) or [M(COD)Cl](2) (M = Pd or Pt) afford bischelated complexes [Rh(CO)Cl{(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (11), and [MCl(2){(t)BuNP(OC(6)H(4)PPh(2)-o)}](2) (12, M = Pd; 13, M = Pt) in good yield. The 1 : 2 reaction between 3 and [PdCl(η(3)-C(3)H(5))](2) in dichloromethane resulted initially in the formation of a tripalladium complex of the type [Pd(3)Cl(4)(η(3)-C(3)H(5))(2){(t)BuNPOC(6)H(4)PPh(2)}(2)] (14a) which readily reacts with moisture to form an interesting binuclear complex, [Cl(2)Pd{μ-(PPh(2)C(6)H(4)OP(μ-(t)BuN)(2)P(O)}(μ-Cl)Pd(OC(6)H(4)PPh(2))] (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 5 with [PdCl(η(3)-C(3)H(5))](2) also affords a binuclear complex [{PdCl(η(3)-C(3)H(5))}(t)BuNH{(t)BuNP}(2)OC(6)H(4)PPh(2){PdCl(2)}] (15) containing a PdCl(2) moiety which forms a six-membered chelate ring via ring-phosphorus and PPh(2) moieties on one side and a PdCl(η(3)-C(3)H(5)) fragment coordinating to amide bound phosphorus atom on the other side of the ring. Treatment of 3 with four equivalents of AuCl(SMe(2)) produces a tetranuclear complex, [(AuCl)(4){(t)BuNP(OC(6)H(4)PPh(2))}(2)] (16), whereas a 1 : 3 reaction between 5 and AuCl(SMe(2)) leads to the formation of a trinuclear complex, [(t)BuNH{(t)BuNP(AuCl)}(2)OC(6)H(4)P(AuCl)Ph(2)] (17). The crystal structures of 3, 5, 9-11 and 13-17 are reported.