José M. Casas

A one-year follow-up study in anorexia nervosa. Dietary pattern and anthropometrical evolution.

Objective: To find out the modifications and the interrelationships between the energy and macronutrient intakes and anthropometric measurements of a group of anorexia nervosa patients (ANP), with homogenous diagnosis, age and treatment, during a 1 y follow-up.Design: Longitudinal study design.Subjects: Fourteen restricting-type ANP in the adolescent age (11–21 y) were recruited for the study and evaluated at four time intervals during 1 y of multidisciplinary treatment: (a) on admission (AN0); (b) after 1 month (AN1); (c) after 6 months (AN6); (d) after 1 y (AN12).Measures: Energy and macronutrient composition of the diet (48 h recall) and anthropometric measurements including skinfold thickness.Results: Mean weight and BMI were under the 3rd percentile in AN0. All anthropometrical parameters increased significantly in AN1 compared to AN0 and did not change in AN6 and AN12. Energy and macronutrient intakes increased significantly in AN1. The dietary changes were not maintained in the subsequent time intervals and there was an overall tendency to turn back to AN0 results. Energy intake adequacy to Spanish Recommended Intakes (RI) showed only an acceptable ratio in AN1 (94% RI); however, a preserved protein intake was found throughout the study (mean intakes between 128.5% and 230.0% RI). Negative correlations were found at AN12 between size of arms subcutaneous fat stores and energy and macronutrient intakes.Conclusion: In this 1 y follow-up study the decrease in the intake of energy and macronutrients after discharge seems to be related to anthropometric evolution, so that a return to restrictive eating behaviour had occurred in those subjects who had reached the highest values in their subcutaneous fat stores, probably related to dissatisfaction with self-body image.European Journal of Clinical Nutrition (2001) 55, 547–554

Neutral and anionic binuclear perhalogenophenyl platinum–silver complexes with Pt→Ag bonds unsupported by covalent bridges. Molecular structures of [(tht)(C6Cl5)(C6F5)2-PtAg(PPh3)], [NBu4][(C6F5)4PtAg(tht)] and [NBu4][cis-(C6Cl5)2(C6F5)2PtAg(tht)](tht = tetrahydrothiophene)

Heterobinuclear complexes of general formula [L(C6Cl5)3-x(C6F5)xPtAg(PPh3)][x= 2–0; L = tht (tetrahydrothiophene), PPh3 or pyridine (py)]14–21 have been prepared by treating the anionic platinum derivatives [NBu4][PtL(C6F5)x(C6Cl5)3-x] with [Ag(OCIO3)(PPh3)](molar ratio 1 : 1) in dichloromethane. The anionic [NBu4][(C6F5)4PtAgL](L = OEt2, PPh3 or tht)22–24 and [NBu4][cis-(C6Cl5)2(C6F5)2PtAg(tht)]25 have been obtained from the corresponding [NBu4]2[Pt(C6X5)2(C6X′5)2] and [Ag(OCIO3)L](molar ratio 1 : 1) in CH2Cl2–diethyl ether. The reaction between [NBu4][Pd(C6F5)3(tht)] and [Ag(OCIO3)(PPh3)] renders Ag(C6F5) and cis-[Pd(C6F5)2(PPh3)(tht)]. The salts [NBu4]2[Pt(C6Cl5)4] and [NBu4]2[Pd(C6F5)4] react with [Ag(OCIO3)(tht)] yielding [NBu4][Pt(C6Cl5)3(tht)] and [NBu4][Pd(C6F5)3(tht)], respectively. The reactions between [NBu4]2[Pt(C6F5)4] and [Ag(OCIO3)(tht)] or [Ag(OCIO3)(PPh3)](molar ratio 1:2) render in the first case complex 24 while in the second an unstable material which evolves to [(Ph3P)(C6F5)3PtAg(PPh3)]27 is obtained. The reaction between [NBu4]2[trans-PtCl2(C6X5)2](X = F or Cl) and [Ag(OCIO3)(tht)] or [Ag(tht)2]ClO4 have also been studied. The structures of [(tht)(C6Cl5)(C6F5)2PtAg(PPh3)]14, [NBu4][(C6F5)4PtAg(tht)]24 and [NBu4][cis-(C6Cl5)2PtAg(tht)]25 have been established by single-crystal X-ray diffraction studies. The complexes contain a strong Pt→Ag bond [2.650(2), 14; 2.641(1), 24; and 2.692(2)A, 25] unsupported by covalent bridges, and short contacts between the o-F or o-Cl atoms of the C6X5(X = F or Cl) groups and the Ag atom are present. The relative strength of such contacts is discussed. Methods for the synthesis of mixed pentachloro-pentafluoro-phenyl starting complexes 1–13 have been investigated.

Synthesis and reactivity of binuclear homo- or hetero-metallic complexes [NBu4]2[MM′(µ-C6F5)2(C6F5)4](M = M′= Pd or Pt; M = Pt, M′= Pd) with bridging pentafluorophenyl groups

By reacting [NBu4]2[M(C6F5)4] with cis-[M(C6F5)2(thf)2](M = Pd or Pt; thf = tetrahydrofuran) in CHCl3 the binuclear homo- or hetero-metallic complexes [NBu4]2[MM′(µ-C6F5)2(C6F5)4](M = M′= Pd or Pt; M = Pt, M′= Pd), containing bridging pentafluorophenyl groups, are obtained. Their structures have been established by 19F n.m.r. spectroscopy. The homometallic derivatives react with neutral (L) or anionic (X)– ligands yielding [NBu4][M(C6F5)3L](M = Pd or Pt; L = PPh3, CO, or ½Ph2PCH2PPh2) or [NBu4]2[MX(C6F5)3](M = Pd or Pt; X = Br), respectively. The heterometallic complex [NBu4]2[PdPt(µ-C6F5)2(C6F5)4] reacts with PPh3 or Ph2PCH2PPh2 giving rise to a mixture of cis-[Pd(C6F5)2L2] and [NBu4]2[Pt(C6F5)4], while its reaction with CO yields a mixture of [NBu4][Pt(C6F5)3(CO)] and [NBu4][Pd(C6F5)3(CO)].

The first structurally characterized complex containing bridging 2,2'-bipyridine. Synthesis and X-ray crystal structure of (PPN)2[Pt(C6F5)3(μ-2,2'-bipy)Pt(C6F5)3]

Abstract The reactions between Q2[Pt2(μ-C6F5)2(C6F5)4] (Q = NBu4, PPN) and 2,2′-bipy (molar ratio 1 : 1) in CH2Cl2 afford the binuclear Q2[(C6F5)3Pt(μ-2,2′-bipy)Pt(C6F5)3] complex, which contains the 2,2′-bipy acting as a bridging ligand. A similar reaction with 1,10-phen renders cis-Pt(C6F5)2phen and Q2[Pt(C6F5)4] (Q =NBu4). On the other hand, (NBu4)2[Pd2(μ-C6F5)2(C6F5)4] reacts in CH2Cl2 with either bipy or phen (NN) (1 : 1), yielding in both cases cis-Pt(C6F5)2(NN) and (NBu4)2[Pd(C6F5)4]. The structure of the binuclear platinum complex (Q = PPN) which contains for the first time a 2,2′-bipy bridging ligand has been determined by X-ray crystallography.

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C6F5)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study

Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.

Symmetric or unsymmetric cleavage of the bridging system in [M2(μ-C6F5)2(C6F5)4]2− (M2Pt2, Pd2 or PtPd) with 2,2′-bipyridine or 1,10-phenanthroline. Molecular structure of [PPN]2[(C6F5)3Pt(μ-bpy)Pt(C6F5)3] and [NBu4][Pt(C6F5)3(phen)]☆

Abstract Binuclear M 2 (MPt, Pd) complexes with bridging NN (NNbpy) [NBu 4 ] 2 [M 2 (μ-NN)(C 6 F 5 ) 6 ], mononuclear Pt complexes with monodentate bpy or phen [NBu 4 ][Pt(C 6 F 5 ) 3 (NN)] or neutral mononuclear Pt complexes with chelating phen [Pt(C 6 F 5 ) 2 (NN)] or Pd complexes with bpy or phen [Pd(C 6 F 5 ) 2 (NN)] can be prepared starting from [NBu 4 ] 2 [M 2 (μ-C 6 F 5 ) 2 (C 6 F 5 ) 4 ] by adequate choice of solvents and reactions conditions. The crystal structures of [PPN] 2 [Pt 2 (μ-bpy)(C 6 F 5 ) 6 ] and [NBu 4 ][Pt(C 6 F 5 ) 3 (phen)] have been established by X-ray crystallography.

Synthesis and structural characterization of platinum and palladium complexes containing O-donor C6X2O42− ligands

Abstract The reactions between (NBu4)2(C6X2O4) (X=HdihydroxybenzoquinonateX=Clchloranilate) and cis-[Pt(C6F5)2(THF)2] in 1:1 molar ratio render the mononuclear complexes [NBu4]2[Pt(C6X2O4)(C6F5)2] (X=H (1)Cl (2)) If the reaction is carried out in 1:2 molar ratio the dinuclear complexes [NBu4]2[M2(μ-C6X2O4)(C6F5)4] (M=PtX=H (3)M=PtX=Cl (4)M=PdX=H (5)M=PdX=Cl (6)) are obtained Complexes 3–6 can also be prepared by reacting C6X2O2(OH)2 with the dinuclear complexes [NBu4]2[M2(μ-C6F5)2(C6F5)4] in molar 1:1 ratio Cyclic voltammetry studies on 3 indicates that these complexes can be reversibly reduced Neverthelessthe reduction products cannot be isolated The oxidation of the platinum complexes 3 and 4 with an excess of Cl2 leads to the synthesis of a mononuclear complex of Pt(IV)(OC-6-31)[NBu4][PtCl3(C6F5)2(H2O)] (7) The molecular structures of 3 and 7 have been determined by single-crystal X-ray diffraction

Synthesis and x-ray structure of [NBu][Pt(CF)(μ-C F) μ-Ag(SC H )] (SC H = tetrahydrothiophene). evidence of the existence of intramolecular AgF interactions in solution and in the solid state

Abstract—The title complex (2) has been synthesized by 1:1 reaction of [NBu][Pt(C F)(μ-C F)] with [Ag(OClO)(SC H)] in CH C1. The structure of 2·0.5C Hhas been determined by single-crystal X-ray diffraction methods. Complex 2 contains two Pt—Ag bonds unsupported by other covalent bridges [Pt(l)—Ag = 2.799(1), Pt(2)—Ag = 2.824(1) ]. The platinum atoms are bridged by two pentafiuorophenyl groups and the silver atom. The bridging pentafiuorophenyl groups are oriented in such a way that the silver atom makes short contacts with two of their ortho-fluorine atoms [AgF(30) = 2.643(5), AgF(32) = 2.716(6) ]. These o-FAg contacts can also be observed in the 19F NMR spectrum of 2. This is the first time that such contacts have been detected in solution. Copyright

Synthesis and molecular structure of trinuclear [trans-Pt(C6Cl5)2{(gm-Cl)AgPPh3}2]

Abstract The title complex has been obtained either by reacting (NBu4)[Cl(C6Cl5)2Pt(μ-Cl)AgPPh3] (1) or (NBu4)2[trans-PtCl2(C6Cl5)2] with (O3ClO)AgPPh3 in 1 : 1 or 1 : 2 molar ratios, respectively. Its structure has been established by X-ray diffraction. The trinuclear compound trans-Pt(C6Cl5)2[(μ-Cl)AgPPh3]2 (2) does not have any Pt Ag bonds so that the AgPPh3 moieties are connected to the platinum fragment through Pt(μ-Cl)Ag bonds. A comparison between the structures of 1 and 2 has been made.

Pentafluorophenylplatinum complexes containing η1- or η2-aryl–Pt interactions. Crystal structure of cis-[Pt(C6F5)2-({NC5H4[CH(η2-Ph)Ph]-2}-κN)]·0.5C6H5Me

The reaction of cis-[Pt(C6F5)2(thf)2]1(thf = tetrahydrofuran) with a 1 : 1 molar ratio of 2-(diphenylmethyl)pyridine or tribenzylamine in CH2Cl2 resulted in displacement of the thf molecules and formation of cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}]2 and cis-[Pt(C6F5)2{N(CH2Ph)3}]3 respectively. The solid-state structure of 2 has been established by X-ray diffraction methods and reveals the existence of a η2-phenyl–Pt interaction which is maintained in solution (NMR). Crystal data for 2·0.5C6H5Me: C33.5H19F10NPt, triclinic, space group P, a= 11.653(4), b= 12.345(3), c= 12.499(4)A, α= 116.91(2), β= 104.33(2), γ= 103.41(2)°, Z= 2, R= 0.038 for 2791 unique ‘observed’ absorption-corrected reflections collected at 233 K. Complexes 2 and 3 reacted with CO yielding cis-[Pt(C6F5)2{NC5H4(CHPh2)-2}(CO)] and cis-[Pt(C6F5)2{N(CH2Ph)3}(CO)] respectively.