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1.
BMC Psychiatry ; 22(1): 135, 2022 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-35189848

RESUMO

BACKGROUND: The integration of a personal recovery-oriented practice in mental health services is an emerging principle in policy planning. Self-management support (SMS) is an intervention promoting recovery that aims at educating patients on the nature of their mental disorder, improving their strategies to manage their day-to-day symptoms, fostering self-efficacy and empowerment, preventing relapse, and promoting well-being. While SMS is well established for chronic physical conditions, there is a lack of evidence to support the implementation of structured SMS programs for common mental disorders, and particularly for anxiety disorders. This study aims to examine the effectiveness of a group-based self-management support program for anxiety disorders as an add-on to treatment-as-usual in community-based care settings. METHODS/DESIGN: We will conduct a multicentre pragmatic randomized controlled trial with a pre-treatment, post-treatment (4-month post-randomization), and follow-ups at 8, 12 and 24-months. TREATMENT AND CONTROL GROUPS: a) group self-management support (10 weekly 2.5-h group web-based sessions with 10-15 patients with two trained facilitators); b) treatment-as-usual. Participants will include adults meeting DSM-5 criteria for Panic Disorder, Agoraphobia, Social Anxiety Disorder, and/or Generalized Anxiety Disorder. The primary outcome measure will be the Beck Anxiety Inventory; secondary outcome measures will comprise self-reported instruments for anxiety and depressive symptoms, recovery, self-management, quality of life, and service utilisation. STATISTICAL ANALYSIS: Data will be analysed based on intention-to-treat with a mixed effects regression model accounting for between and within-subject variations in the effects of the intervention. DISCUSSION: This study will contribute to the limited knowledge base regarding the effectiveness of structured group self-management support for anxiety disorders. It is expected that changes in patients' self-management behaviour will lead to better anxiety management and, consequently, to improved patient outcomes. TRIAL REGISTRATION: ClinicalTrials.gov: NCT05124639 . Prospectively registered 18 November 2021.


Assuntos
Transtorno de Pânico , Autogestão , Adulto , Agorafobia/terapia , Transtornos de Ansiedade/psicologia , Transtornos de Ansiedade/terapia , Doença Crônica , Humanos , Estudos Multicêntricos como Assunto , Qualidade de Vida , Ensaios Clínicos Controlados Aleatórios como Assunto , Resultado do Tratamento
2.
J Altern Complement Med ; 23(5): 326-330, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28384006

RESUMO

OBJECTIVES: Human immunodeficiency virus (HIV) infection is a stressful disease, and depression is the most common form of psychologic distress experienced by those infected. The aim of this study was to further develop and validate a mind-body intervention to improve coping self-efficacy strategies and increase mental health. DESIGN: Feasibility study, a randomized trial. Participants were assigned into two blocks (female/male) and simple randomization in a 1:1 ratio was performed within each block to one of two arms (1) intervention group, (2) control group who received usual care. Setting/Location and Subjects: The authors enrolled 30 HIV-infected individuals (10 women and 20 men) who had psychologic challenges and were motivated for working with personal development at the Department of Infectious Diseases at Aarhus University Hospital, Denmark. INTERVENTION: The intervention was a group intervention facilitated by an educated coach. The framework was a 3-day residential course plus two single-day/8-h follow-up events. The intervention was based primarily on a Native American philosophy of life and its understanding of how changes affect human beings and create imbalance. OUTCOME MEASURES: Primary outcomes were change in risk of depression and level of coping self-efficacy. Secondary outcomes were change in levels of stress and personal growth. RESULTS: Significant improvement between the intervention group and control group was seen in risk of depression and personal growth mean values from baseline to 6-month follow-up. Significant improvements were shown within the intervention group in mean values of risk of depression, coping self-efficacy, stress, and personal growth. There were no significant improvements within the control group. CONCLUSIONS: The authors suggest that interventions designed to increase resilience through enhancing coping self-efficacy be used in conjunction with HIV medication to make this approach and especially the "whole-person" commitment a fully integrated aspect of HIV care.


Assuntos
Adaptação Psicológica/fisiologia , Depressão/terapia , Infecções por HIV/psicologia , Terapias Mente-Corpo , Autoeficácia , Adulto , Aconselhamento , Estudos de Viabilidade , Feminino , Humanos , Masculino , Adulto Jovem
3.
Arch Suicide Res ; 18(4): 340-62, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24846577

RESUMO

The objective of this study was to review the literature and make suggestions for further investigation into the topic of professionals' reactions following a patient's suicide. An extensive search of the literature has been undertaken using computer database search. Even if findings are heterogenous, most studies suggest limited stress-related or affective-related reactions for the majority of respondents. Whereas, findings with regards to the impact on professional practice are consistent in identifying important consequences in the way professionals conduct their clinical assessment and reach treatment decisions after a patient's suicide. Future research should investigate how this event changes the clinician's personal growth and capacity to establish a therapeutic alliance with other suicidal patients.


Assuntos
Atitude do Pessoal de Saúde , Transtornos Mentais , Suicídio/psicologia , Humanos , Transtornos Mentais/diagnóstico , Transtornos Mentais/psicologia , Transtornos Mentais/terapia , Relações Profissional-Paciente , Processos Psicoterapêuticos
4.
J Aggress Maltreat Trauma ; 20(3): 304-321, 2011 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-23687441

RESUMO

Until recently, only one study was published on cognitive-behavioral therapy (CBT) of posttraumatic stress disorder (PTSD) in individual therapy via videoconference (Germain, Marchand, Bouchard, Drouin, & Guay, 2009); however, it only assessed the posttreatment effect. This study presents the follow-up of Germain et al.'s (2009) study. The main goal was to compare the effectiveness after six months of CBT for PTSD either face-to-face (n = 24) or by videoconference (n = 12). Each participant received CBT for 16 to 25 weeks and completed various questionnaires before and after treatment and at a six-month follow-up. The two treatments had equivalent levels of symptom reduction (Modified PTSD Symptom Scale: η2 < 0.01, p > .05) and proportion of patients with a clinically significant change in symptoms (42% for face-to-face vs. 38% for videoconferencing, p > .05). Thus, CBT for PTSD via videoconference seems to be a viable alternative when adequate face-to-face treatments are less available.

5.
Cyberpsychol Behav Soc Netw ; 13(1): 29-35, 2010 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-20528290

RESUMO

Telepsychotherapy is a cutting-edge intervention that shows great promise in the mental health care field. However, the possibility of developing a high-quality therapeutic alliance is often doubted when psychotherapy is provided remotely. This study assesses the development of a therapeutic alliance in individuals with posttraumatic stress disorder who were treated either by videoconference therapy or a face-to-face therapy. Forty-six participants with PTSD received cognitive behavioral therapy, 17 of them by videoconference and 29 in person. A variety of questionnaires evaluating the quality of the therapeutic relationship were administered at five different times during treatment. Each session was also assessed by the therapist and the participant immediately afterwards. The results indicate that a therapeutic alliance can develop very well in both treatment conditions and that there is no significant difference between the two. Certain clinical and practical implications are discussed.


Assuntos
Terapia Cognitivo-Comportamental/métodos , Relações Profissional-Paciente , Consulta Remota , Transtornos de Estresse Pós-Traumáticos/terapia , Adolescente , Adulto , Idoso , Análise de Variância , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Inquéritos e Questionários , Resultado do Tratamento , Comunicação por Videoconferência
6.
Cogn Behav Ther ; 38(1): 42-53, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19235601

RESUMO

Telehealth, or health care via videoconferencing, constitutes a clinical option that makes it possible to treat patients remotely. A growing number of studies have demonstrated that telehealth is a feasible and effective method for diagnostic interviews and psychiatric consultations. However, few studies have assessed the effectiveness of psychotherapy given by videoconference. This study examines the effectiveness of cognitive behavioural therapy (CBT) administered by videoconference for posttraumatic stress disorder (PTSD). Forty-eight participants with PTSD were recruited for the study: 16 in the videoconferencing condition and 32 in a control face-to-face condition. Each participant received CBT for 16 to 25 weeks and completed various questionnaires before and after treatment. The results show a significant decline in the frequency and severity of posttraumatic symptoms after treatment in both conditions. A clinical improvement in overall functioning was also observed. No significant difference was observed in the effectiveness of the two therapeutic conditions. The examination of effect sizes supports these results. A number of clinical implications and certain avenues for future research are discussed.


Assuntos
Terapia Cognitivo-Comportamental/métodos , Consulta Remota , Transtornos de Estresse Pós-Traumáticos/terapia , Adaptação Psicológica , Adulto , Feminino , Seguimentos , Humanos , Entrevista Psicológica , Masculino , Pessoa de Meia-Idade , Aceitação pelo Paciente de Cuidados de Saúde , Inventário de Personalidade , Transtornos de Estresse Pós-Traumáticos/diagnóstico , Transtornos de Estresse Pós-Traumáticos/psicologia , Resultado do Tratamento
7.
Bioorg Med Chem Lett ; 15(6): 1693-5, 2005 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-15745823

RESUMO

A novel class of macrocyclic 1,6-napthyridines designed to adopt the presumed bioactive conformation of anti-HCMV acyclic 1,6-napthyridines are described. Both 14- and 15-membered macrocycles were shown to be highly potent against HCMV HSV-1 and HSV-2.


Assuntos
Antivirais/química , Antivirais/farmacologia , Citomegalovirus/efeitos dos fármacos , Naftiridinas/química , Naftiridinas/farmacologia , Antivirais/síntese química , Desenho de Fármacos , Herpesvirus Humano 1/efeitos dos fármacos , Herpesvirus Humano 2/efeitos dos fármacos , Humanos , Modelos Químicos , Modelos Moleculares , Estrutura Molecular , Naftiridinas/síntese química
8.
Inorg Chem ; 43(10): 3127-35, 2004 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-15132618

RESUMO

The dimers [Cu(2)(dppm)(2)(CN-t-Bu)(3)](BF(4))(2) and [Ag(2)(dppm)(2)(CN-t-Bu)(2)](X)(2) (X(-) = BF(4)(-), ClO(4)(-)) and the coordination polymers [[M(diphos)(CN-t-Bu)(2)]BF(4)](n) (M = Cu, Ag; diphos = bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph)), [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n), and [[Ag(dpppen)(CN-t-Bu)]BF(4)](n) have been synthesized and fully characterized as model materials for the mixed bridging ligand polymers which exhibit the general formula [[M(diphos)(dmb)]BF(4)](n) (M = Cu, Ag; dmb = 1,8-diisocyano-p-menthane) and [[Ag(dppm)(dmb)]ClO(4)](n). The identity of four polymers ([[Ag(dppb)(CN-t-Bu)(x)]BF(4)](n) (x = 1, 2), [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n), [[Ag(dppm)(dmb)]ClO(4)](n)) and the two dimers has been confirmed by X-ray crystallography. The structure of [[Ag(dppm)(dmb)]ClO(4)](n) exhibits an unprecedented 1-D chain of the type "[Ag(dmb)(2)Ag(dppm)(2)(2+)](n)", where d(Ag(.)Ag) values between tetrahedral Ag atoms are 4.028(1) and 9.609(1) A for the dppm and dmb bridged units, respectively. The [[Ag(dppb)(CN-t-Bu)(x)]BF(4)](n) polymers (x = 1, 2) form zigzag chains in which the Ag atoms are tri- and tetracoordinated, respectively. The [[Ag(2)(dppb)(3)(CN-t-Bu)(2)](BF(4))(2)](n) polymer, which is produced from the rearrangement of [[Ag(dppb)(CN-t-Bu)(2)]BF(4)](n), forms a 2-D structure described as a "honeycomb" pattern, where large [Ag(dppb)(+)](6) macrocycles each hosting two counterions and two acetonitrile guest molecules are observed. Properties such as glass transition temperature, morphology, thermal decomposition, and luminescence in the solid state at 293 K are reported. The luminescence bands exhibit maxima between 475 and 500 nm with emission lifetimes ranging between 6 and 55 micros. These emissions are assigned to a metal-to-ligand charge transfer (MLCT) of the type M(I) --> pi(NC)/pi(PPh(2)).

9.
Bioorg Med Chem Lett ; 13(21): 3847-51, 2003 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-14552793

RESUMO

Rigidified derivatives have been designed and synthesized assuming the g+t conformer of acetylcholine (N-C-C-O=+60 degrees, C-C-O-C=180 degrees ) as active conformation for binding to cytisine sensitive neuronal nicotinic receptors. The SAR of the compounds evaluated, along with those of more flexible analogues, support the g+t conformer hypothesis and highlight the stringent steric limitation of this nicotinic receptor sub-type. Compound 3e has low microM affinity for cytisine sensitive nicotinic receptor binding sites while being selective with regard to the alpha-bungarotoxin sensitive subclass. We also report few compounds with microM affinity for the alpha-bungarotoxin sensitive subclass.


Assuntos
Acetilcolina/química , Neurônios/metabolismo , Receptores Nicotínicos/efeitos dos fármacos , Acetilcolina/metabolismo , Alcaloides/farmacologia , Animais , Azocinas/farmacologia , Bungarotoxinas/farmacologia , Desenho de Fármacos , Cromatografia Gasosa-Espectrometria de Massas , Técnicas In Vitro , Indicadores e Reagentes , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Mimetismo Molecular , Neurônios/efeitos dos fármacos , Prosencéfalo/efeitos dos fármacos , Prosencéfalo/metabolismo , Quinolizinas/farmacologia , Ensaio Radioligante , Ratos , Relação Estrutura-Atividade
10.
J Org Chem ; 67(16): 5486-96, 2002 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-12153246

RESUMO

Cyclononanes from the 7 low-energy conformational archetypal families (twist-boat[bond]chair, twist-chair[bond]boat, twist-chair[bond]chair, twist-chair[bond]twist-chair, skew-chair[bond]boat, skew-chair[bond]chair, and skew-boat[bond]boat) were transformed into 12 of 13 MM3 stochastically generated cis-cyclononenes. This was done by systematically converting single bond synclinal endocyclic torsion angles, one-at-a-time, into double-bond synperiplanar analogues, followed by geometry optimization [e.g. density functional theory B3LYP/6-31G(d)]. Torsion angles adjacent to the new double bond maintained their signs, while their magnitudes usually changed considerably to accommodate the new neighboring synperiplanar torsion angles. The six remaining torsion angles all maintained their signs and approximate magnitudes compared to corresponding values in the seven saturated parent structures. As a result, the same "twist"/"skew" conformational descriptors previously used for the saturated conformers can now also be applied to the corresponding unsaturated analogues. Three conformational families have multiple members (subtypes) in which the double bond is located at different positions on the same ring conformation. The solid-state structures of (+/-)-1-phenyl-1,3,4,5,6,7-hexahydro-2,6-benzoxazonine-6-carbonitrile (22) and (1RS,3SR)-1-phenyl-3-methyl-1,3,4,5,6,7-hexahydro-2,6-benzoxazonine-6-carbonitrile (23) were determined by single-crystal X-ray diffraction analysis. The asymmetric unit of the Ponemacr; unit cell for 22 contains two symmetry-unrelated molecules, both of which exhibit a skew-chair-boat (SCBtype-2) conformation identical to that found for crystalline 23. This subtype has yet to be found in the Cambridge Crystallographic DataBase. Crystal lattice packing considerations alone cannot explain the observation of the SCBtype-2 conformation since (1)H NMR spectroscopy shows the same conformational bias when the crystals are dissolved in CDCl(3).

12.
Inorg Chem ; 38(5): 957-963, 1999 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-11670868

RESUMO

The title compounds [Pt(4)(dmb)(4)(PPh(3))(2)]Cl(2) (1) and {[Pt(4)(dmb)(4)(diphos)]Cl(2)}(n)() (diphos = dppb (2), dppp (3), dpph (4)) have been prepared in good yields from the reaction of Pt(2)(dba)(3).CHCl(3) with 2 equiv of dmb and 1 equiv of PPh(3) for 1 (dba = dibenzylideneacetone) and from the reactions of Pt(2)(dba)(3).CHCl(3) with 2 equiv of dmb and 0.5 equiv of diphos for 2-4. The structure for 1 consists of a quasi-linear Pt(4)L(2)(2+) species (L = PPh(3); d(PtPt) = 2.666(2), 2.655(2), 2.641(2) Å), where the dmb ligands bridge the Pt atoms forming a catenate. From Raman spectroscopy, the two nu(PtPt) active modes for 1 are observed at 162 and 84 cm(-)(1) (F(PtPt) = 2.36 mdyn Å(-)(1)). For 2-4, the diphos ligands induce the formation of amorphous polymeric materials (X-ray powder diffraction patterns) with MW ranging from 84 000 to 307 000 according to viscometry. EHMO calculations predict that the HOMO and LUMO are the two dsigma orbitals arising from four interacting Pt atoms via the d(x)()()2(-)(y)()()2, d(z)()()2, s, and p(x)() M atomic orbitals. These are mixed with the ddelta and CNR(pi) MO's. From the examination of the position, absorptivity, and fwhm (full width at half maximum) of the strongly allowed low-energy UV-vis band, a dsigma --> dsigma assignment is made (lambda(max) = 405 nm, epsilon = 35 800 M(-)(1) cm(-)(1); EtOH for 1). The four compounds are luminescent at 77 K in EtOH, where lambda(emi) are 750, 736, 750, and 755 nm and tau(e) are 2.71, 4.78, 5.15, and 5.17 ns for 1-4, respectively. On the basis of the Stokes shifts (10 000-12 000 cm(-)(1)) and the long emission lifetimes, a phosphorescence dsigma --> dsigma assignment is made for the observed emissions. Crystal data for 1: crystal system triclinic; space group P1; a = 12.624(4) Å; b = 14.24(2) Å; c = 27.312(3) Å; alpha = 92.35(3) degrees; beta = 91.655(15) degrees; gamma = 90.28(5) degrees; V = 4903(7) Å(3); Z = 2; D(calc) = 1.528 g cm(-)(3); R(1) = 0.0738; wR(2) = 0.2097; S = 1.018.

13.
Inorg Chem ; 38(6): 1253-1260, 1999 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-11670910

RESUMO

Direct reactions of the AgY salts with dmb (1,8-diisocyano-p-menthane) in a 1:1 stoichiometric amount generate the binuclear Ag(2)(dmb)(2)Y(2) complexes. The X-ray crystallography establishes that the structure consists of two Ag(+) atoms bridged by two dmb ligands forming a 20-membered ring and by two counteranions via one of the O-atoms, forming a four-membered ring (local symmetry = D(2)(h)()). The Ag(I).Ag(I) separations are 3.909(1) and 3.6831(8) Å for Y = NO(3)(-) and CH(3)CO(2)(-), respectively. Reactions of Ag(2)(dmb)(2)Y(2) (Y = NO(3)(-), ClO(4)(-)) with LiTCNQ lead to the paramagnetic tetranuclear species [Ag(4)(dmb)(4)(TCNQ)(3)]TCNQ. The structure at 180 K consists of two Ag(2)(dmb)(2)(2+) species (d(Ag.Ag) = 4.113(1) Å held together by three parallel TCNQ(-)'s, with Ag(+).N&tbd1;C distances ranging from 2.359(5) to 2.787(5) Å. Two of the Ag(+) atoms are tricoordinated, and the other two are tetracoordinated placed within in a centrosymmetric geometry. The three bridging TCNQ(-)'s exhibit interplanar distances of 3.333(1) Å, and the Ag(4) species are packed side-by-side with two adjacent TCNQ(-)'s face-to-face (separation = 3.372(1) Å) forming an infinite pi-stacked chain TCNQ(-)'s. The TCNQ(-) counteranion also exhibits weak pi-contacts via the -CN groups with other counteranions. The magnetic susceptibilities, EPR spectra, and unit cell parameters have been measured as a function of temperature. The magnetic data are best explained by extended chains of antiferromagnetically coupled S = (3)/(2) and S = (1)/(2) centers for the [Ag(4)(dmb)(4)(TCNQ)(3)](+) and TCNQ(-) moieties, respectively. No hyperfine structure has been observed between 106 and 290 K, indicating the presence of rapid exchange in the paramagnetic system. Crystal data: Ag(2)(dmb)(2)(NO(3))(2), crystal system, orthorhombic, space group = C(cmb), a = 8.6464(15) Å, b = 16.375(3) Å, c = 20.663(5) Å, Z = 4; Ag(2)(dmb)(2)(O(2)CCH(3))(2).2H(2)O, crystal system triclinic, space group P&onemacr;, a = 9.1175(9) Å, b = 9.1451(10) Å, c = 11.7247(8) Å, alpha = 80.294(7) degrees, beta = 71.124(7) degrees, gamma = 64.258(8) degrees, Z = 1; [Ag(4)(dmb)(4)(TCNQ)(3)]TCNQ, crystal system triclinic, space group = P&onemacr;, a = 9.9837(12) Å, b = 13.5194(14) Å, c = 17.1788(9) Å, alpha = 99.423(6) degrees, beta = 101.512(8) degrees, gamma = 96.917(11) degrees, Z = 1.

14.
Inorg Chem ; 38(6): 1305-1315, 1999 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-11670918

RESUMO

The title compounds [Pd(4)(dmb)(4)(PPh(3))(2)]Cl(2) (1) and {[Pd(4)(dmb)(5)](CH(3)CO(2))(2)}(n)() (2) were prepared from the reactions Pd(2)(dba)(3).CHCl(3) + 2dmb + PPh(3) for 1 (dba = dibenzylideneacetone) and Pd(2)(dba)(3).S + excess dmb + Pd(O(2)CCH(3))(2) for 2 (S = benzene or CHCl(3)), in good yields. The stuctures consist of quasi-linear Pd(4)(2+) species (d(PdPd) = 2.524(10), 2.524(10) and 2.534(10) Å for 1 and 2.5973(18), 2.6080(18), and 2.6080(18) Å for 2) where the dmb ligands bridge the Pd atoms, forming a catenate. While the PPh(3) ligands axially coordinate the M(4) structure in 1, a fifth dmb bridges another Pd(4)(dmb)(5)(2+) species, forming an organometallic polymer. From Raman spectroscopy, the two nu(PdPd) active modes (nu(1) and nu(2)) are observed at 165 and 86 cm(-)(1), respectively, for 1 (F(PdPd) = 1.44 mdyn Å(-)(1)). On the basis of EHMO (extended Hückel molecular orbital calculations), we predict that the HOMO and LUMO are the two dsigma orbitals arising from four interacting Pd atoms via the d(x)()()2(-)(y)()()2, d(z)()()2, and p(x)() M atomic orbitals. This assignment is confirmed by the UV-vis spectra, in particular from the second-moment band analysis, which indicates that the two Franck-Condon active modes are modes with frequencies of 165 and 86 cm(-)(1), which are assigned to nu(PdPd). The compounds exhibit luminescence at 77 K with lifetimes in the microsecond regime. During the course of this study, use of TCNQ(0) (tetracyanoquinodimethane) as the oxidizing agent during the reaction (instead of CHCl(3) or Pd(O(2)CCH(3))(2)) leads to 3 ([Pd(2)(dmb)(4)(&mgr;-Cl)](TCNQ)(3)), which is the first encapsulated halide ion "M(2)(dmb)(4)" species that is characterized from X-ray crystallography (d(PdCl) = 2.7143(6) Å). X-ray data for 2.4H(2)O: monoclinic, P2(1)/c, a = 19.433(2) Å, b = 15.312(2) Å, c = 29.156(2) Å, beta = 98.841(10) degrees, V = 8572.7(15) Å(3), Z = 4. X-ray data for 3: triclinic, P&onemacr;, a = 13.314(2) Å, b = 13.490(2) Å, c = 14.645(2) Å, alpha = 108.267(10) degrees, beta = 104.834(10) degrees, gamma = 101.221(10) degrees, V = 2303.8(6) Å(3), Z = 1.

15.
Inorg Chem ; 38(22): 4928-4936, 1999 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-11671233

RESUMO

The title compound is prepared from the direct reaction of Pt(2)(dba)(3) (dba = dibenzylideneacetone) and [Au(PPh(3))(2)](PF(6)) in the presence of 1,8-diisocyano-p-methane (dmb), with Pt(2)(dmb)(2)Cl(2), [Pt(4)(dmb)(4)(PPh(3))(2)](PF(6))(2), and (PPh(3))AuCl being formed as parallel products. X-ray crystallography reveals the presence of a quasi-linear PPh(3)Au-AuPPh(3) fragment encapsulated inside a "Pt(2)(dmb)(2)(2+)" ring which is axially coordinated with two PPh(3) ligands. The d(AuAu) is 2.5977(6) Å and is indicative of a strong Au-Au single bond. The IR nu(CN) data reveal that the Pt oxidation state is I, which places the Au oxidation state at 0. The PtAu distances are 2.8422(5) and 2.8082(5) Å. The Raman-active nu(Au(2)), nu(PtAu) (b(2g) + a(g)), nu(PtP), nu(AuP), and nu(PtC) are found at 121.2, approximately 100, 85.5, 162.1, 183.1, and 457.2, and 440.9 cm(-)(1), respectively. The PtAu (0.67 mdyn Å(-)(1)) and Au(2) (1.21 mdyn Å(-)(1)) force constants (F) confirm the presence of medium PtAu and strong Au(2) bonding interactions. The absorption spectra are characterized by strong bands at lambda(max) (epsilon, M(-1) cm(-1)) at 316 (32 300), 366 (37 800), and 418 nm (21 500) and lower intensity features at 516 (2860) and 655 nm (834). The cluster is luminescent at low temperatures (solid and frozen glasses), and in the solid state at room temperature, and exhibits an emission band at approximately 875 nm, and an emission lifetime, tau(e), of 4.4 +/- 0.4 ns (solvent = butyronitrile, T = 77 K).

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