Environmental Enrichment Preceding Early Adulthood Methylphenidate Treatment Leads to Long Term Increase of Corticosterone and Testosterone in the Rat

Attention-deficit/hyperactivity disorder (ADD/ADHD) has been emerging as a world-wide psychiatric disorder. There appears to be an increasing rate of stimulant drug abuse, specifically methylphenidate (MPH) which is the most common treatment for ADHD, among individuals who do not meet the criteria for ADHD and particularly for cognitive enhancement among university students. However, the long term effects of exposure to MPH are unknown. Thus, in light of a developmental approach in humans, we aimed to test the effects of adolescence exposure to enriched environment (EE) followed by MPH administration during early adulthood, on reactions to stress in adulthood. Specifically, at approximate adolescence [post natal days (PND) 30–60] rats were reared in EE and were treated with MPH during early adulthood (PND 60–90). Adult (PND 90–92) rats were exposed to mild stress and starting at PND 110, the behavioral and endocrine effects of the combined drug and environmental conditions were assessed. Following adolescence EE, long term exposure to MPH led to decreased locomotor activity and increased sucrose preference. EE had a beneficial effect on PPI (attentive abilities), which was impaired by long term exposure to MPH. Finally, the interaction between EE and, exposure to MPH led to long-term elevated corticosterone and testosterone levels. In view of the marked increase in MPH consumption over the past decade, vigilance is crucial in order to prevent potential drug abuse and its long term detrimental consequences

Synthesis and molecular structure of 1,3-di-tert-butyl-2,4-bis(cyclodipentadienyl)iron(II) 1,3,2,4-diazadiphosphetidine, [Fe(eta(5)-C5H4)(2)((PNBu)-Bu-t)(2)]

The reaction of the dichlorocyclodiphosphazane (also called dichlorodiazadiphosphetidine), [ClP(mu-(NBu)-Bu-t)](2), with in situ generated ferrocene dilithiate in a 1:1 molar ratio affords the first metallocene derivative of a diazadiphosphetidine, 1,3-di-tert-butyl-2,4-bis(cyclopentadienyl)iron(II) 1,3,2,4-diazadiphosphetidine, [Fe(eta(5)-C5H4)(2)((PNBu)-Bu-t)(2)], in good yield

Group 11 metal chemistry of a tetradentate ligand, phenylene-1,4-diaminotetra(phosphonite), p-c(6)h(4)[n{p(oc(6)h(4)ome-o)(2)}(2)](2)

The Cu(I), Ag(I), and Au(I) chemistry of a tetradentate ligand (phenylene-1,4-diaminotetra(phosphonite), p-C(6)H(4)[N{P(OC(6)H(4)OMe-o)(2)}(2)](2) (P(2)N Phi NP(2)) (1)) is described. The flexional conformations in 1 leads to interesting structural variations in transition-metal complexes. The reaction of 1 with 4 equiv of CuX (where X = Br and I) produce the tetranuclear complexes, [{Cu(2)(mu-X)(2)(NCCH(3))(2)}(2)(mu-P(2)N Phi NP(2))] (where X = Br (2) or X = 1 (3)) in quantitative yield. Treatment of 3 with an excess of pyridine, 2-(piperazin-1-yl)pydmidine, and pyrazole yielded the tetra-substituted derivatives, [{Cu(2)(mu-I)(2)(L)(2)}(2)(mu-P(2)N Phi NP(2))1 (where L = pyridine (4), 2-(piperazin-1-yl)pydmidine (5), or pyrazole.(6)). Similar reactions of 3 with 1,10-phenanthroline (phen) and 2,2'-bipyridine in a 1:2 molar ratio afford the disubstituted derivatives, [(Cu(2)(mu-I))(2)l(2)(phen)(2)(mu-P(2)N Phi NP(2))] (7) and [(Cu(2)(mu-I))(2)l(2)(bipy)(2)(mu-P(2)N Phi NP(2))] (8). The o-methoxyphenoxy substituents on phosphorus in complexes 5 and 7 adopt approximately parallel planar conformations and contain lattice solvents. The reaction of 3 with 1,4-diazabicyclo[2.2.2]octane (DABCO) in a 1:2 molar ratio in a dichloromethane-acetonitrile mixture leads to the formation of an ionic complex [N(CH(2)CH(2))(3)N(+)CH(2)Cl](2)[(Cu(2)(Cl)(I)(2))(2)(NCCH(3))(2)(mu-p2N Phi NP(2))](2-) (9), as a result of the chloromethylation of DABCO. Treatment of 1 with 4 equiv of AgClO(4) produces [{Ag(2)(mu-ClO(4))(2))(2)(C(4)H(8)O)(2)}(2)(mu-P(2)N Phi NP(2))] (10). Displacement of perchlorate ions in 10 by PhN{P(OC(6)H(4)OMe-o)(2)}(2) (PNP) or 2,2'-bipyridine yielded [(mu-PNP)(2)Ag(2)(mu-P(2)N Phi NP(2))Ag(2)- (mu-PNP)(2)](ClO(4))(4) (11) and [{Ah(2)(bipy)(2)}(2)(mu-P(2)N Phi NP(2))](ClO(4))(4) (12), respectively. The similar reaction of 1 with 2 equiv of AgOTf, in the presence of 4,4'-bipyridine, gave a three-dimensional Ag(I) coordination polymer, [{Ag(2)(C(10)H(8)N(2))(2) (CH(3)CN)(2)}(2)(P(2)N Phi NP(2))](n)(OTf)(4n) (13). The reactions of 1 with [AuCl(SMe(2))], in appropriate ratios, afford the tetranuclear and dinuclear complexes, [(Au(2)Cl(2))(2)(mu-P(2)N Phi NP(2))] (14) and [(AuCl)(2)(P(2)N Phi NP(2))] (15). Complex 14 undergoes moisture-assisted P-N bond cleavage in the presence of PhN{P(OC(6)H(4)OMe-o)(2))(2) to give [p-NH(2)C(6)H(4)N(P(OC(6)H(4)OMe-o)(2)}(2)Au(2)Cl(2)] (17) and [PhN{P(OC(6)H(4)OMe-o)(2)}(2)Au(2)Cl(2)]. The strucures of the complexes 5, 7-10, 12-15, and 17 are confirmed by single-crystal X-ray diffraction studies

Di-, tetra- and polynuclear Rh(I) complexes containing phenylene-1,4-diaminotetra(phosphonite), p-C(6)H(4)[N{P(OC(6)H(4)OMe-o)(2)}(2)](2) and their catalytic investigation towards transfer hydrogenation reactions

The reactions of phenylene-1,4-diaminotetra(phosphonite), p-C(6)H(4)[N{P(OC(6)H(4)OMe-o)(2)}(2)](2) (P(2)N(Ph)NP(2)) (1) with [Rh(COD)Cl](2) in 1 : 2 and 1 : 1 molar ratio produce tetra- and polymetallic chelate complexes, [Rh(4)(COD)(2)(mu-Cl)(4)(P(2)N(Ph)NP(2))] (2) and[Rh(2)(mu-Cl)(2)(P(2)N(Ph)NP(2))](n) (3), respectively. Similar reaction of 1 with [Rh(COD)Cl](2) in dichloromethane-acetonitrile mixture furnishes a dinuclear complex, [Rh(2)Cl(2)(CH(3)CN)(2)(P(2)N(Ph) NP(2))] (4). The reaction of 3 or 4 with CO affords a dinuclear carbonyl derivative, [Rh(2)Cl(2)(CO)(2)(P(2)N(Ph)NP(2))] (5). Treatment of 4 with 2 equivalents of pyrazine or 4,4'-bipyridine produce one-dimensional Rh(I) coordination polymers, [Rh(2)Cl(2)(C(4)H(4)N(2))(P(2)N(Ph) NP(2))](n) (6) and [Rh(2)Cl(2)(C(10)H(8)N(2))(P(2)N(Ph) NP(2))](n) (7) in quantitative yields. The catalytic activity of RhI complexes 2-7 have been investigated in transfer hydrogenation reactions

A cyclodiphosphazane based pincer ligand, [2,6-{mu-((BuN)-Bu-t)(2)P((BuHN)-Bu-t)PO}(2)C6H3I]: Ni-II, Pd-II, Pt-II and Cu-I complexes and catalytic studies

Synthesis and late-transition metal complexes of pincer capable cyclodiphosphazane, 2,6-{mu-((BuN)-Bu-t)(2)P-((BuHN)-Bu-t)PO}(2)C6H3I (1) are described. The condensation of 2-iodoresorcinol with cis-{ClP(mu-(NBu)-Bu-t)(2)PN(H)Bu-t} produced a difunctional derivative 1 in good yield. The treatment of Ni(COD)(2), Pd-2(dba)(3)center dot CHCl3 or Pt(PPh3)(4) with 1 afforded pincer complexes [2,6-{mu-((BuN)-Bu-t)(2)P((BuHN)-Bu-t)PO}(2)C6H3MI] (2 M = Ni; 3 M = Pd and 4 M = Pt). The reaction of complex 3 with copper halides resulted in the formation of heterobimetallic complexes bridged by rhombic {Cu(mu-X)}(2) units, [{{Cu(mu-X)}(2)}{mu-((BuN)-Bu-t)(2)P((BuHN)-Bu-t)PO}(2)C6H3PdI] (5 X = I and 6 X = Br). The crystal structures of 1-3, 5 and 6 were established by single X-ray diffraction studies. The palladium complex 3 was tested for catalytic P-arylation of diphenylphosphine oxide (Ph2P(O)H) under microwave irradiation. Moderate to good catalytic activity was observed with aryl bromides

Transition metal chemistry of large-bite bisphosphines, N,N-bis(diphenylphosphinobenzyl)-N-phenylamine and bis(2-diphenylphosphinobenzyl)ether

Oxidation reactions and transition metal chemistry of large bite bisphosphines N,N-bis(diphenylphosphinobenzyl)-N-phenylamine (1) and bis(2-diphenylphosphinobenzyl)ether (2) are described. The reactions of 1 and 2 with chalcogenides in 1:2 M ratios afforded bis-chalcogenides. Reactions of 1 and 2 with M(COD)Cl-2 (M = Pd, Pt) in 1:1 M ratios yielded trans-[MCl2{C6H5N(CH2-2-C6H4PPh2)(2)}-kappa P-2,P] (M = Pd, 9; Pt, 10) and cis-[MCl2{O(CH2-2-C6H4PPh2)(2)}-kappa P-2,P] (M = Pd, 11; Pt, 12), respectively. Treatment of 1 and 2 with [Pd(eta(3)-C3H5)Cl](2) and [RuCl2(eta(6)-p-cymene)](2) in 1:1 M ratios produced dinuclear complexes of the type [Pd2Cl2(eta(3)-C3H5)(2)-mu-{C6H5N(CH2-2-C6H4PPh2)(2)}-mu P,P] (13), [Pd2Cl2(eta(3)-C3H5)(2)-mu-{O(CH2-2-C6H4PPh2)(2)}-mu P,P] (14), [{Ru(eta(6)-p-cymene)}(2)-mu-{C6H5N(CH2-2-C6H4PPh2)(2)}-mu P,P] (17) and [{Ru(eta(6)-p-cymene)}(2)-mu-{O(CH2-2-C6H4PPh2)(2)}-eta P,P] (18). The reactions of 1 and 2 with one half equivalent of [Pd(eta(3)-C3H5)Cl](2) followed by the addition of AgOTf yielded chelate complexes [Pd(eta(3)-C3H5){C6H5N(CH2-2-C6H4PPh2)(2)}-kappa P-2,P]OTf (15) and [Pd(eta(3)-C3H5){O(CH2-2-C6H4PPh2)(2)}-kappa P-2,P]OTf (16). The reactions of 1 and 2 with [AuCl(SMe2)] in 1: 2 and 1: 1 M ratios afforded dinuclear [(Au2Cl2)C6H5N(CH2-2-C6H4PPh2)(2)-mu-P,P] (19), [Au2Cl2O(CH2-2-C6H4PPh2)(2)-mu-P,P] (20) and mononuclear complexes [(AuCl)C6H5N(CH2-2-C6H4PPh2)(2)-kappa P-2,P] (21), [(AuCl)O(CH2-2-C6H4PPh2)(2)-kappa P-2,P] (22), with the ligands exhibiting bridging and chelating modes of coordination. The crystal structures of 3, 7, 8, 11, 12, 15 and 19 have been established by X-ray diffraction studies. (C) 2016 Elsevier B.V. All rights reserved

Tris(4-methylpiperazin-1-yl)phosphane, P(NC4H8NMe)(3): Synthesis, structural studies, group 10 and 11 metal complexes and catalytic investigations

Group 10 and 11 metal complexes of a multidentate phosphorus-nitrogen donor ligand tris(4-rnethylpiperazin-1-yl)phosphane, P(NC4H8NMe)(3) (1) are reported. The reactions of 1 with an equimolar amount of CuX (X = Cl, Br and I) afford tetranuclear cubane-like complexes [(CuX){P(NC4H8NMe)(3)}](4) (2, X = Cl; 3, X = Br and 4, X = I) in excellent yield. Treatment of 1 with AuCl(SMe2) produces a mononuclear complex, [(AuCl){P(NC4H8NMe)(3)}] (5). Reaction of 1 with AgCN produces a 2D Ag-I polymeric sheet, [(AgCN)(2){P(NC4H8NMe)(3)}](n) (6) in moderate yield. The similar 1:1 reactions of I with AgX (X = Cl and Br) furnish dinuclear complexes, [(AgX){P(NC4HBNMe)(3)}](2) (7, X = Cl and 8, X = Br). The 2:1 reactions of 1 with [M(COD)Cl-2] (M = Pd or Pt) afford [{P(NC4H8NMe)(3)}(2)MCl2] (9, M = Pd and 10, M = Pt) in quantitative yield. The molecular structures of complexes 1-3 and 6 are established through single-crystal X-ray diffraction studies. The catalytic activity of the Pd-II complex 9 has been investigated in Suzuki cross coupling reactions. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Bis(2-diphenylphosphinoxynaphthalen-1-yl)methane: transition metal chemistry, Suzuki cross-coupling reactions and homogeneous hydrogenation of olefins

Transition metal complexes of bis(2-diphenylphosphinoxynaphthalen-1-yl) methane (1) are described. Bis(phosphinite) 1 reacts with Group 6 metal carbonyls, [Rh(CO)(2)Cl](2), anhydrous NiCl2, [Pd(C3H5)Cl](2)/AgBF4 and Pt(COD)I-2 to give the corresponding 10-membered chelate complexes 2, 3 and 5-8. Reaction of 1 with [Rh(COD)Cl](2) in the presence of AgBF4 affords a cationic complex, [Rh(COD){Ph2P(-OC10H6)(mu-CH2)(C10H6O-)PPh2-kappa P, kappa P}]BF4 (4). Treatment of 1 with AuCl(SMe2) gives mononuclear chelate complex, [(AuCl){Ph2P(-OC10H6)(mu-CH2)(C10H6O-) PPh2-kappa P, kappa P}] (9) as well as a binuclear complex, [Au(Cl){mu-Ph2P(-OC10H6)(mu-CH2)(C10H6O-) PPh2- kappa P, kappa P} AuCl] (10) with ligand 1 exhibiting both chelating and bridged bidentate modes of coordination respectively. The molecular structures of 2, 6, 7, 9 and 10 are determined by X-ray studies. The mixture of Pd(OAc)(2) and 1 effectively catalyzes Suzuki cross-coupling reactions of a range of aryl halides with aryl boronic acid in MeOH at room temperature or at 60 degrees C, giving generally high yields even under low catalytic loads. The cationic rhodium(I) complex, [Rh(COD){Ph2P(-OC10H6)(mu-CH2)(C10H6O-) PPh2-kappa P, kappa P}]BF4 (4) catalyzes the hydrogenation of styrenes to afford the corresponding alkyl benzenes in THF at room temperature or at 70 degrees C with excellent turnover frequencies

Diamondoid-Type Copper Coordination Polymers Containing Soft Cyclodiphosphazane Ligands

Three novel coordination polymers have been synthesized by reacting cis- and trans-alkyne-appended cydodiphosphazanes with CuX (X = Br, I) salts. The reaction of cis-[(PhC CP)(2)(mu-(NBu)-Bu-t)(2)] (1) with CuBr in a 1:3 molar ratio gave a 3D coordination polymer, [{Cu-4(mu(3)-Br)(4)}{(cis-(PhC CP)(2)(mu-(NBu)-Bu-t)(2))-Cu-4(mu(2)-Br)(4)(cis-(PhC CP)(2)(mu-(NBu)-Bu-t)}(2))(4)](n) (3), having diamondoid topology with an unprecedented copper alkyne coordination, whereas the reaction of 1 with CuI in a 1:4 molar ratio afforded a ID polymeric complex, [{Cu-4(mu(3)-I)(4)}(NCCH3)(2){cis-(PhC CP)(2)(mu-(NBu)-Bu-t)(2)}](n)(4). In contrast, the reaction of trans-[(PhC CP)(2)(mu-(NBu)-Bu-t)(2)] (2) with CuI was found to be independent of stoichiometry and afforded a 3D coordination polymer, [{Cu-4(mu(3)-I)(4)4}{trans-(PhC CP)(2)(mu-(NBu)-Bu-t)(2)}(2)](n) (5), exclusively

Gold(I) complexes of cyclodiphosphazanes cis-{RP(mu-N(t)Bu)}(2): structure of a novel tetranuclear gold(I) macrocycle, [{Au{(o-MeOC(6)H(4)O)P(mu-N(t)Bu)}(2)}(4)](ClO(4))(4)

Reactions of two equivalents of [AuCl(SMe(2))] with cyclodiphosphazanes cis-{RP(m-N(t)Bu)}(2) (1a-1d) produce binuclear gold(I) complexes of the type, [ClAu{RP(m-N(t)Bu)}(2)AuCl] (2 R = OC(6)H(4)OMe-o, 3 R = OCH(2)CH(2)OMe, 4 R = NEt(2), 5 R = NH(t)Bu) in quantitative yield. A similar reaction between cis-{(o-MeOC(6)H(4)O)P(mu-N(t)Bu)}(2) (1a) and [AuCl(SMe2)] in a 1 : 1 molar ratio afforded the mono-nuclear complex [ClAu{(o-MeOC(6)H(4)O) P(mu-N(t)Bu)}(2)] (6). Addition of two equivalents of CuX (X = Br, I) to the chloro derivative 2 leads to the formation of bromo, [BrAu{(o-MeOC(6)H(4)O)-P(mu-N(t)Bu)}(2)AuBr] (7), and iodo, [IAu{(o-MeOC(6)H(4)O) P(mu-N(t)Bu)}(2)AuI] (8), derivatives through halogen exchange reactions. A tetranuclear gold(I) macrocycle [Au{(o-MeOC(6)H(4)O)P(mu-N(t)Bu)}(2)](4)-(ClO(4))(4) (9) and a mononuclear gold(I) complex [Au({(o-MeOC(6)H(4)O)P(mu-N(t)Bu)}(2))(2)]ClO(4) (10) were obtained, respectively, from 1 : 1 and 2 : 1 stoichiometric reactions between 1a and [Au(SMe(2))(2)]ClO(4). Molecular structures of complexes 4, 6, 7, 8 and 9 are confirmed by single-crystal X-ray diffraction studies. Interestingly, the crystal structure of the tetra-nuclear Au(I) macrocycle 9 reveals the encapsulation of one ClO(4)(-) anion inside the bowl shaped macrocyclic cavity through weak Au center dot center dot center dot O and C-H center dot center dot center dot O interactions