Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles.

Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ and κ complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand.

Intramolecularly stabilised group 10 metal stannyl and stannylene complexes: multi-pathway synthesis and observation of platinum-to-tin alkyl transfer.

Reaction of [PdClMe(P^N)2] with SnCl2 followed by Cl-abstraction leads to apparent Pd-C bond activation, resulting in methylstannylene species trans-[PdCl{(P^N)2SnClMe}][BF4] (P^N = diaryl phosphino-N-heterocycle). In contrast, reaction of Pt analogues with SnCl2 leads to Pt-Cl bond activation, resulting in methylplatinum species trans-[PtMe{(P^N)2SnCl2}][BF4]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated.

Palladium-catalyzed dehydrostannylation of n-alkyltin trichlorides.

[Pd(PPh(3))(4)] catalyzes the dehydrostannylation of n-alkyltin trichlorides into HSnCl(3)(THF)(n) and isomers of the corresponding alkene. The reaction mechanism involves oxidative addition of the Sn-C bond followed by β-H elimination from the resulting n-alkylpalladium trichlorostannyl species. Rate-determining reductive elimination of HSnCl(3) from cis-[PdH(SnCl(3))(PPh(3))(2)] completes the catalytic cycle.

Dichlorostannylene complexes of group 10 metals, a unique bonding mode stabilized by bridging 2-pyridyldiphenylphosphine ligands.

The reaction of tin dichloride with catalytically-relevant group 10 metal precursors [M(Cl)(X)(2-PyPPh(2))(2)] (M = Ni, Pd, Pt; 2-PyPPh(2) = 2-pyridyldiphenylphosphine; X = Cl, Me) provides easy access to unprecedented cationic dichlorostannylene complexes [M(X)(2-PyPPh(2))(2)(SnCl(2))](+) where the M-Sn bond is bridged by two head-to-head coordinated 2-PyPPh(2) ligands. The formation of such species instead of the classical neutral trichlorostannyl derivatives [M(X)(SnCl(3))(2-PyPPh(2))(2)] offers a new insight on the specific effect of the SnCl(2) cocatalyst in group 10 metal catalyzed transformations.

Psychosocial and cognitive rehabilitation of patients with solvent-induced chronic toxic encephalopathy: a randomised controlled study.

Background: There is little experience with the (neuro) psychological treatment of patients with solvent-induced chronic toxic encephalopathy (CSE). In this randomised controlled trial (RCT), a treatment programme was evaluated based on previous outcome studies of patients with chronic fatigue, whiplash and traumatic brain damage.

Methods: The treatment consisted of 8 group sessions based on cognitive behavioural principles focusing on inadequate illness behaviours, and 8 sessions of cognitive strategy training to compensate memory problems.

The course of apraxia and ADL functioning in left hemisphere stroke patients treated in rehabilitation centres and nursing homes.

Objective: To study the course of apraxia and daily life functioning (ADL) in left hemisphere stroke patients with apraxia.

Design: Prospective cohort study.

Setting: Rehabilitation centres and nursing homes.

Cognitive functioning in patients with suspected chronic toxic encephalopathy: evidence for neuropsychological disturbances after controlling for insufficient effort.

Objectives: Chronic toxic encephalopathy (CTE) caused by long term occupational exposure to organic solvents is still a controversial disorder. Neuropsychological testing is the cornerstone for diagnosing the syndrome, but can be negatively influenced by motivational problems. In this nationwide study, we investigated the neuropsychological functioning and psychological symptoms of a large group of patients with suspected CTE, and ruled out alternative explanations for their complaints, including suboptimal performance due to insufficient effort.

Discomfort and factual recollection in intensive care unit patients.

Introduction: A stay in the intensive care unit (ICU), although potentially life-saving, may cause considerable discomfort to patients. However, retrospective assessment of discomfort is difficult because recollection of stressful events may be impaired by sedation and severe illness during the ICU stay. This study addresses the following questions.

Parallel synthesis and study of fluorous biphasic partition coefficients of 1H,1H,2H,2H-perfluoroalkylsilyl derivatives of triphenylphosphine: a statistical approach.

A library of fluorous, (1H,1H,2H,2H-perfluoroalkyl)silyl-substituted derivatives of triphenylphosphine, Ph(3-a)P[C(6)H(5-y)[SiMe(3-b)(CH(2)CH(2)C(x)F(2x+1))(b)](y)-pos](a) [a = 1-3; b = 1-3; x = 4, 6, 8, or 10; pos = 3, 4 (y = 1) or 3,5 (y = 2)], was prepared using parallel synthetic techniques. Upon variation of these four parameters, a total of 108 different fluorous phosphines can be synthesized. Using factorial design, 37 phosphines were selected and their partition coefficients in the typical fluorous biphasic solvent system PFMCH/toluene (PFMCH = perfluoromethylcyclohexane) determined.

Psychological treatment of patients with chronic toxic encephalopathy: lessons from studies of chronic fatigue and whiplash.

Background: Chronic toxic encephalopathy (CTE), which can result from long-term exposure to organic solvents, is characterized by problems of attention and memory, fatigue and affective symptoms. There is little experience with (neuro)psychological treatment in this patient group. We reviewed treatment outcome studies of CTE and comparable syndromes, namely, chronic whiplash-associated disorder (WAD) and chronic fatigue syndrome (CFS), with a view to providing recommendations for the psychological treatment of patients with CTE.

Suboptimal performance on neuropsychological tests in patients with suspected chronic toxic encephalopathy.

Suboptimal performance during neuropsychological testing can seriously complicate assessment in behavioral neurotoxicology. We present data on the prevalence of suboptimal performance in a group of Dutch patients with suspected chronic toxic encephalopathy (CTE) after long-term occupational exposure to solvents. One hundred and forty-five subjects referred to one of two Dutch national assessment centers for CTE were administered the Amsterdam Short-Term Memory Test (ASTM) and the Test of Memory Malingering (TOMM), two tests specifically developed for the detection of suboptimal performance.

Subjective changes in emotion, cognition and behaviour after stroke: factors affecting the perception of patients and partners.

The presence and severity of changes in emotion and cognition experienced by left- and right-sided stroke patients and observed by their partners were compared at 3 months poststroke. The results showed that, regardless of the side of stroke, several changes were reported by half of the stroke patients and their partners. It appeared that while left hemisphere stroke patients agreed with their partners on the number and severity of most changes, partners of right hemisphere patients reported more frequent and more severe changes than the patients themselves.

1H,1H,2H,2H-perfluoroalkyl-functionalization of Ni(II), Pd(II), and Pt(II) mono- and diphosphine complexes: minimizing the electronic consequences for the metal center.

A series of fluorous derivatives of group 10 complexes MCl(2)(dppe) and [M(dppe)(2)](BF(4))(2) (M = Ni, Pd or Pt; dppe = 1,2-bis(diphenylphosphino)ethane) and cis-PtCl(2)(PPh(3))(2) was synthesized. The influence of para-(1H,1H,2H,2H-perfluoroalkyl)dimethylsilyl-functionalization of the phosphine phenyl groups of these complexes, as studied by NMR spectroscopy, cyclovoltammetry (CV), XPS analyses, as well as DFT calculations, points to a weak steric and no significant inductive electronic effect. The steric effect is most pronounced for M = Ni and leads in the case of NiCl(2)(1c) (3c) and [Ni(1c)(2)](BF(4))(2) (7c) (1c = [CH(2)P[C(6)H(4)(SiMe(2)CH(2)CH(2)C(6)F(13))-4](2)](2)) to a tetrahedral distortion from the expected square planar geometry.

Speed of information processing after unilateral stroke.

Speed of information processing in the subacute stage after stroke was studied in 88 first ever, unilateral, ischemic stroke patients. The patient group included 42 right and 46 left hemisphere patients. Seventy-one control subjects were also examined.

A highly fluorous room-temperature ionic liquid exhibiting fluorous biphasic behavior and its use in catalyst recycling.

[formula: see text] A novel fluorous room-temperature ionic liquid, 1-butyl-3-methyl-imidazolium tetrakis[p-[dimethyl(1H, 1H, 2H, 2H-perfluorooctyl)silyl]phenyl]-borate (1), was used as a solvent for the homogeneous hydrosilylation of 1-octene catalyzed by a fluorous version of Wilkinson's catalyst. The catalyst was recycled by biphasic separation with an average retention of catalyst activity of 94%. As opposed to other ionic liquids, 1 exhibits high miscibility with apolar compounds such as alkenes and resembles fluorous solvents in its phase behavior with organic solvents.

Platinum- and palladium-catalysed Kocheshkov redistribution of dialkyltin dichlorides or tetraalkyltins with tin tetrachloride.

The Kocheshkov redistribution reaction of tetraalkyltin or dialkyltin dichlorides with tin tetrachloride is effectively catalysed by platinum(II) or palladium(II) phosphine complexes, yielding alkyltin trichlorides in high yield and with high selectivity.

Sensitivity of different ADL measures to apraxia and motor impairments.

Objective: To determine whether specifically designed activities of daily living (ADL) observations can measure disability due to apraxia with more sensitivity than the Barthel ADL Index, a conventional functional scale.

Design: Cross-sectional study.

Setting: Rehabilitation centres and nursing homes.

No major cognitive impairment in young children with acute lymphoblastic leukemia using chemotherapy only: a prospective longitudinal study.

Purpose: To study, using serial neuropsychological assessment and evaluation of school achievement, persistent neuropsychological late effects in children treated for acute lymphoblastic leukemia (ALL) at a young age with chemotherapy only.

Patients And Methods: Twenty consecutive patients underwent three evaluations, including 12 psychometric measures beside IQ. The authors applied strict methodology and a prospective-longitudinal design that started at diagnosis and extended to a median follow-up of 7 years.

Relations between subjective evaluations of memory and objective memory performance.

Several explanations for the weak relations between subjective memory judgements and objective memory performance were investigated in two groups of normal older adults. Group 1 sampled a general population (mean age 61.6 yr.

Construct validity of concepts of attention in healthy controls and patients with CHI.

The present study aimed to examine the construct validity of three aspects of attention, namely focused, divided, and supervisory control of attention. Factor-analytic techniques were applied to scores of healthy subjects on a series of neuropsychological tests tapping these aspects of attention. The two components found did not match the hypothesized aspects and were labeled as Memory-driven Action and Stimulus-driven Reaction.

[Cognitive impairments among older drivers: medical examination and driving test].

The aim of this study was to gain insight in the prevalence of cognitive impairments among active older drivers and in driving performance of cognitively impaired ones. The study was implemented in the existing Dutch relicensing procedure for older drivers and consisted of three evaluation moments: a medical screening (for all subjects), a neuropsychological assessment and a test-drive (for candidates with cognitive impairments). In total, 2992 drivers were medically evaluated.

Slight cognitive impairment and magnetic resonance imaging abnormalities but normal school levels in children treated for acute lymphoblastic leukemia with chemotherapy only.

Objectives: To investigate persistent neuropsychologic late effects in children treated for acute lymphoblastic leukemia at a young age with chemotherapy only by means of serial neuropsychologic assessments (NPAs), magnetic resonance imaging (MRI) of the brain, and evaluation of school levels.

Study Design: Consecutive patients (n = 17) had 2 extensive NPAs (12 psychometric measures) after cessation of therapy. Test results were compared with those of both healthy control subjects and 28 previously treated children who received cranial irradiation.

[Memory strategies of elderly: training efficacy].

Does memory strategy training improve the quantity and quality of reported strategy use of normal older adults (N = 111, mean age 63 years, range 46-85 years) in daily life? Three strategy training conditions, remembering names (N = 26), intentions (N = 20) and verbal information (N = 20) and an educational training (N = 23) were compared to a test-retest control group (N = 22). Strategy use was assessed with a Strategy Frequency Questionnaire (investigating the reported frequency of strategy use on five scales: encoding, retrieval, general, external and no strategies) and a Memory Situations Questionnaire (investigating the preference of strategies in specific situations). Three months after training, the frequency of strategy use as assessed by the scale scores had not increased more in the strategy training conditions than in the control condition.