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1.
Clin J Sport Med ; 34(1): 25-29, 2024 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-37462603

RESUMEN

OBJECTIVE: Previous research, including high-quality systematic reviews, has found that cervical injury, which often accompanies concussive head injury, can delay recovery from concussion. One pilot randomized controlled trial found that focused cervical assessment and appropriate intervention in children and young adults with persisting postconcussive symptoms (PPCS) improved recovery outcomes. Our sports medicine clinics adopted this approach early (within 2 weeks) in children (aged 10-18 years) after concussion. This study describes our clinical management protocol and compares the recovery trajectories in children after concussion with and without a concomitant cervical injury. DESIGN: Prospective cohort study. SETTING: Three university-affiliated outpatient sports medicine clinics from September 2016 to December 2019. PATIENTS: One-hundred thirty-four concussed children with cervical impairment (mean age 14.9 years, 65% male, and 6.2 days since concussion) were compared with 130 concussed children without cervical impairment (mean age 14.9 years, 57% male, and 6.0 days since concussion). INDEPENDENT VARIABLES: Examination findings related to the cervical spine (range of motion, cervical spasm, and cervical tenderness). MAIN OUTCOME MEASURES: Recovery time (measured in days), concussion symptom burden (Postconcussion Symptom Scale), and incidence of PPCS. RESULTS: Children with cervical impairment reported a higher initial symptom burden; however, there were no differences in recovery time (33.65 [28.20-39.09] days vs 35.98 [27.50-44.45] days, P = 0.651) or incidence of PPCS (40.0% vs 34.3%, P = 0.340). CONCLUSIONS: We conclude that within this pediatric population, early identification and management of cervical injuries concomitant with concussion may reduce the risk of delayed recovery.


Asunto(s)
Traumatismos en Atletas , Conmoción Encefálica , Síndrome Posconmocional , Adulto Joven , Humanos , Niño , Masculino , Adolescente , Femenino , Síndrome Posconmocional/diagnóstico , Síndrome Posconmocional/terapia , Síndrome Posconmocional/epidemiología , Estudios Prospectivos , Conmoción Encefálica/complicaciones , Conmoción Encefálica/diagnóstico , Conmoción Encefálica/terapia , Medición de Riesgo , Traumatismos en Atletas/complicaciones , Traumatismos en Atletas/diagnóstico , Traumatismos en Atletas/terapia
2.
Sci Rep ; 13(1): 4615, 2023 03 21.
Artículo en Inglés | MEDLINE | ID: mdl-36944682

RESUMEN

Pathogens with persistent environmental stages can have devastating effects on wildlife communities. White-nose syndrome (WNS), caused by the fungus Pseudogymnoascus destructans, has caused widespread declines in bat populations of North America. In 2009, during the early stages of the WNS investigation and before molecular techniques had been developed to readily detect P. destructans in environmental samples, we initiated this study to assess whether P. destructans can persist in the hibernaculum environment in the absence of its conclusive bat host and cause infections in naive bats. We transferred little brown bats (Myotis lucifugus) from an unaffected winter colony in northwest Wisconsin to two P. destructans contaminated hibernacula in Vermont where native bats had been excluded. Infection with P. destructans was apparent on some bats within 8 weeks following the introduction of unexposed bats to these environments, and mortality from WNS was confirmed by histopathology at both sites 14 weeks following introduction. These results indicate that environmental exposure to P. destructans is sufficient to cause the infection and mortality associated with WNS in naive bats, which increases the probability of winter colony extirpation and complicates conservation efforts.


Asunto(s)
Ascomicetos , Quirópteros , Hibernación , Animales , Quirópteros/microbiología , Animales Salvajes , Síndrome
3.
Br J Sports Med ; 55(24): 1427-1433, 2021 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-34510003

RESUMEN

OBJECTIVE: The Buffalo Concussion Physical Examination (BCPE) is a brief, but pertinent physical examination designed for the subacute, outpatient assessment of concussion. The purpose of this study was to perform the BCPE on a larger sample and derive a scoring system to identify children at risk for Persistent Post-Concussive Symptoms (PPCS, recovery ≥30 days). METHODS: This prospective, observational cohort study from September 2016 to March 2019 was performed at three university-affiliated concussion clinics. Male and female children (n=270, 14.92±1.86 years, range 8-18, 38% female) were diagnosed with a concussion within 14 days of injury and followed-up until recovery. Logistic regression was used with history and physical examination variables to predict PPCS and a weighted scoring metric was derived. RESULTS: Out of 15 predictor variables, the main effects of 1 preinjury variable (≥3 previous concussions), 2 injury characteristic variables (days-since-injury and type-of-injury), 3 physical examination variables (orthostatic intolerance (OI), vestibulo-ocular reflex (VOR) and tandem gait) and 2 interaction terms (OI/VOR and tandem gait/type-of-injury) produced a score that was 85% accurate for identifying children with low-risk, medium-risk and high-risk for PPCS on cross-validation. CONCLUSION: The Risk for Delayed Recovery (RDR)-Score allows physicians in an outpatient setting to more accurately predict which children are at greater risk for PPCS early after their injury, and who would benefit most from targeted therapies. The RDR-Score is intended to be used as part of a comprehensive assessment that should include validated symptom checklists, mental health history and adjunct testing (eg, cognitive or physical exertion) where clinically indicated.


Asunto(s)
Conmoción Encefálica , Síndrome Posconmocional , Conmoción Encefálica/diagnóstico , Femenino , Marcha , Humanos , Masculino , Síndrome Posconmocional/diagnóstico , Estudios Prospectivos , Riesgo
4.
JAMA Pediatr ; 173(4): 319-325, 2019 04 01.
Artículo en Inglés | MEDLINE | ID: mdl-30715132

RESUMEN

Importance: Sport-related concussion (SRC) is a significant public health problem without an effective treatment. Objective: To assess the effectiveness of subsymptom threshold aerobic exercise vs a placebo-like stretching program prescribed to adolescents in the acute phase of recovery from SRC. Design, Setting, and Participants: This multicenter prospective randomized clinical trial was conducted at university concussion centers. Male and female adolescent athletes (age 13-18 years) presenting within 10 days of SRC were randomly assigned to aerobic exercise or a placebo-like stretching regimen. Interventions: After systematic determination of treadmill exercise tolerance on the first visit, participants were randomly assigned to a progressive subsymptom threshold aerobic exercise or a progressive placebo-like stretching program (that would not substantially elevate heart rate). Both forms of exercise were performed approximately 20 minutes per day, and participants reported daily symptoms and compliance with exercise prescription via a website. Main Outcomes and Measures: Days from injury to recovery; recovery was defined as being asymptomatic, having recovery confirmed through an assessment by a physician blinded to treatment group, and returning to normal exercise tolerance on treadmill testing. Participants were also classified as having normal (<30 days) or delayed (≥30 days) recovery. Results: A total of 103 participants were included (aerobic exercise: n = 52; 24 female [46%]; stretching, n = 51; 24 female [47%]). Participants in the aerobic exercise group were seen a mean (SD) of 4.9 (2.2) days after the SRC, and those in the stretching group were seen a mean (SD) of 4.8 (2.4) days after the SRC. There were no differences in age, sex, previous concussions, time from injury, initial symptom severity score, or initial exercise treadmill test and physical examination results. Aerobic exercise participants recovered in a median of 13 (interquartile range [IQR], 10-18.5) days, whereas stretching participants recovered in 17 (IQR, 13-23) days (P = .009 by Mann-Whitney test). There was a nonsignificant lower incidence of delayed recovery in the aerobic exercise group (2 participants [4%] in the aerobic group vs 7 [14%] in the placebo group; P = .08). Conclusions and Relevance: This is, to our knowledge, the first RCT to show that individualized subsymptom threshold aerobic exercise treatment prescribed to adolescents with concussion symptoms during the first week after SRC speeds recovery and may reduce the incidence of delayed recovery. Trial Registration: ClinicalTrials.gov identifier: NCT02710123.


Asunto(s)
Traumatismos en Atletas/rehabilitación , Conmoción Encefálica/rehabilitación , Terapia por Ejercicio , Ejercicio Físico , Adolescente , Conmoción Encefálica/etnología , Femenino , Humanos , Masculino , Estudios Prospectivos , Recuperación de la Función , Resultado del Tratamiento
5.
Clin J Sport Med ; 29(5): 353-360, 2019 09.
Artículo en Inglés | MEDLINE | ID: mdl-30239422

RESUMEN

OBJECTIVE: To study the effect of early prescribed aerobic exercise versus relative rest on rate of recovery in male adolescents acutely after sport-related concussion (SRC). DESIGN: Quasi-experimental design. SETTING: University sports medicine centers. PARTICIPANTS: Exercise group (EG, n = 24, 15.13 ± 1.4 years, 4.75 ± 2.5 days from injury) and rest group (RG, n = 30, 15.33 ± 1.4 years, 4.50 ± 2.1 days from injury). INTERVENTIONS: Exercise group performed a progressive program of at least 20 minutes of daily subthreshold aerobic exercise. Rest group was prescribed relative rest (no structured exercise). Both groups completed daily online symptom reports (Postconcussion Symptom Scale) for 14 days. MAIN OUTCOME MEASURES: Days to recovery after treatment prescription. Recovery was defined as return to baseline symptoms, exercise tolerant, and judged recovered by physician examination. RESULTS: Recovery time from initial visit was significantly shorter in EG (8.29 ± 3.9 days vs 23.93 ± 41.7 days, P = 0.048). Mixed-effects linear models showed that all symptom clusters decreased with time and that there was no significant interaction between treatment group and time. No EG participants experienced delayed recovery (>30 days), whereas 13% (4/30) of RG participants experienced delayed recovery. CONCLUSIONS: These preliminary data suggest that early subthreshold aerobic exercise prescribed to symptomatic adolescent males within 1 week of SRC hastens recovery and has the potential to prevent delayed recovery.


Asunto(s)
Traumatismos en Atletas/terapia , Conmoción Encefálica/terapia , Ejercicio Físico , Descanso , Adolescente , Humanos , Masculino , Síndrome Posconmocional/terapia , Volver al Deporte
6.
Clin J Sport Med ; 28(1): 13-20, 2018 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-29257777

RESUMEN

OBJECTIVE: To evaluate (1) systematic assessment of exercise tolerance in adolescents shortly after sport-related concussion (SRC) and (2) the prognostic utility of such assessment. DESIGN: Prospective randomized controlled trial. SETTING: University and community sports medicine centers. PARTICIPANTS: Adolescents with SRC (1-9 days from injury). Sixty-five were randomized and 54 completed the study (mean age 15 years, 4 days after injury). INTERVENTIONS: Buffalo Concussion Treadmill Test (BCTT, n = 27) or not (controls, n = 27) on visit day #1. Heart rate threshold (HRt) at symptom exacerbation represented level of exercise tolerance. Participants reported symptoms daily for 14 days and then had follow-up BCTT (n = 54). Recovery was defined as returning to normal level of symptoms and exercise tolerance, verified by independent physician examination. MAIN OUTCOME MEASURES: Days to recovery and typical (≤21 days) versus prolonged recovery (>21 days). Mixed effects linear models and linear regression techniques examined symptom reports and time to recovery. Linear regression assessed the association of HRt with recovery time. RESULTS: Days to recovery (P = 0.7060) and typical versus prolonged recovery (P = 0.1195) were not significantly different between groups. Symptom severity scores decreased in both groups over 14 days (P < 0.0001), were similar (P = 0.2984), and did not significantly increase the day after the BCTT (P = 0.1960). Lower HRt on visit day #1 was strongly associated with prolonged recovery time (P = 0.0032). CONCLUSIONS: Systematic evaluation of exercise tolerance using the BCTT within 1 week after SRC did not affect recovery. The degree of early exercise intolerance after SRC was important for prognosis. This has implications for school academic and team preparation.


Asunto(s)
Traumatismos en Atletas/diagnóstico , Conmoción Encefálica/diagnóstico , Prueba de Esfuerzo/métodos , Tolerancia al Ejercicio , Adolescente , Femenino , Humanos , Modelos Lineales , Masculino , Pronóstico , Estudios Prospectivos
8.
Clin Pediatr (Phila) ; 54(10): 961-8, 2015 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-26084537

RESUMEN

The primary objective of this study was to determine factors in the clinic setting associated with concussion-related problems in the school setting. A total of 91 student athletes, 13 to 19 years old, completed the SCAT2 and computerized testing during their initial visit to the clinic. During a follow-up telephone interview, one-third reported problems with return to school. The presence of problems reported in school was associated with severity of concussion as represented by recovery time and the overall number of symptoms at the first clinic visit. Gender, age, and previous concussions were not associated with school problems. Athletes with computerized test scores below the ninth percentile were more likely to report school problems. The current study offers some descriptive information for clinicians and ideas for future research related to adolescent athletes with concussion and problems with return to the classroom.


Asunto(s)
Traumatismos en Atletas/fisiopatología , Conmoción Encefálica/fisiopatología , Absentismo , Adolescente , Traumatismos en Atletas/rehabilitación , Conmoción Encefálica/rehabilitación , Estudios de Seguimiento , Humanos , Entrevistas como Asunto , Modelos Logísticos , Masculino , Curva ROC , Recurrencia , Adulto Joven
9.
Northeast Nat (Steuben) ; 21(4): N56-N59, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-26229422

RESUMEN

Reduced populations of Myotis lucifugus (Little Brown Myotis) devastated by white-nose syndrome (WNS) persist in eastern North America. Between 2009 and 2013, we recaptured 113 marked individuals that survived between 1 and 6 winters in New England since the arrival of WNS. We also observed signs of reproductive success in 57 recaptured bats.

10.
Clin J Sport Med ; 24(2): 128-33, 2014 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-24184849

RESUMEN

OBJECTIVE: To evaluate return to play (RTP) and return to classroom outcomes when the Zurich guidelines are combined with a standardized exercise treadmill test [Buffalo Concussion Treadmill Test (BCTT)] and computerized neuropsychological (cNP) testing in adolescent athletes after concussion. DESIGN: Retrospective chart review and follow-up. SETTING: University Sports Medicine Concussion Clinic. PARTICIPANTS: One hundred seventeen athletes (75% male) with sport concussion ages 13 to 19 years and telephone follow-up of 91 (77.8%) athletes and their parents. INTERVENTIONS: Concussed athletes who were asymptomatic at rest completed Automated Neuropsychological Assessment Metrics or Immediate Post-concussion Assessment and Cognitive Test cNP testing followed by the BCTT on the same day. Athletes then followed the Zurich consensus guidelines for RTP. MAIN OUTCOME MEASURES: The primary outcome measure was the degree of success in RTP, that is, RTP with or without return of concussive symptoms. Secondary outcome measure was return to school with or without symptoms. RESULTS: All athletes returned to sport without exacerbation of symptoms. Telephone follow-up revealed that 38.5% experienced new issues upon return to the classroom. Forty-eight percent of athletes had 1 or more cNP subtests below average (

Asunto(s)
Traumatismos en Atletas/diagnóstico , Conmoción Encefálica/diagnóstico , Prueba de Esfuerzo , Guías de Práctica Clínica como Asunto , Recuperación de la Función , Adolescente , Traumatismos en Atletas/psicología , Atención , Conmoción Encefálica/psicología , Femenino , Humanos , Masculino , Pruebas Neuropsicológicas , Estudios Retrospectivos , Instituciones Académicas , Adulto Joven
11.
PLoS One ; 7(6): e38920, 2012.
Artículo en Inglés | MEDLINE | ID: mdl-22745688

RESUMEN

White-nose syndrome (WNS), an emerging infectious disease that has killed over 5.5 million hibernating bats, is named for the causative agent, a white fungus (Geomyces destructans (Gd)) that invades the skin of torpid bats. During hibernation, arousals to warm (euthermic) body temperatures are normal but deplete fat stores. Temperature-sensitive dataloggers were attached to the backs of 504 free-ranging little brown bats (Myotis lucifugus) in hibernacula located throughout the northeastern USA. Dataloggers were retrieved at the end of the hibernation season and complete profiles of skin temperature data were available from 83 bats, which were categorized as: (1) unaffected, (2) WNS-affected but alive at time of datalogger removal, or (3) WNS-affected but found dead at time of datalogger removal. Histological confirmation of WNS severity (as indexed by degree of fungal infection) as well as confirmation of presence/absence of DNA from Gd by PCR was determined for 26 animals. We demonstrated that WNS-affected bats aroused to euthermic body temperatures more frequently than unaffected bats, likely contributing to subsequent mortality. Within the subset of WNS-affected bats that were found dead at the time of datalogger removal, the number of arousal bouts since datalogger attachment significantly predicted date of death. Additionally, the severity of cutaneous Gd infection correlated with the number of arousal episodes from torpor during hibernation. Thus, increased frequency of arousal from torpor likely contributes to WNS-associated mortality, but the question of how Gd infection induces increased arousals remains unanswered.


Asunto(s)
Ascomicetos/patogenicidad , Quirópteros/microbiología , Quirópteros/fisiología , Hibernación/fisiología , Nariz/microbiología , Animales , Femenino , Masculino , Piel/microbiología
12.
Br J Sports Med ; 45(6): 492-7, 2011 May.
Artículo en Inglés | MEDLINE | ID: mdl-20484317

RESUMEN

BACKGROUND: Youth ice hockey injury rates and mechanisms have been described by various classification systems. Intentional versus unintentional contact was used to classify mechanisms of injuries. All injuries (n=247) in one youth hockey programme over a 5-year period were recorded and included in the analysis. PURPOSE: To evaluate youth ice hockey injuries and compare programmes that allow body checking versus programmes that do not allow body checking. A primary goal was to determine whether programmes that allow body checking have increased injury rates from intentional body contact. Another goal was to describe the rates of injury across ages, levels of competitive play and during games versus practices. METHODS: Rates of injury were compared for three levels of competition (house, select and representative) for approximately 3000 boys aged 4-18 years over a 5-year period. This represents 13 292 player years. Data were collected prospectively in this cohort study. All injuries were reported prospectively by a designated team official and verified by a physician. The log injury rate (per 1000 player hours) was modelled via Poisson regression with log player hours used as an offset. Rate ratio was used to explain the covariate-adjusted injury rate for each of three groups (all injuries, intentional injuries, unintentional injuries). RESULTS: Unintentional contacts accounted for 66.0% of overall injuries (95% CI 60.0 to 72.0), compared with 34.0% from intentional contacts (p<0.001; Z=5.25). Serious injuries (fractures, dislocations, concussions) resulted more often from unintentional collisions (p=0.04). Players in more competitive leagues that allow body checking had a greater incidence of total injuries than less competitive leagues. CONCLUSIONS: Most injuries in the youth hockey programme studied were the result of unintentional contact, and were generally more severe. These findings were not expected given previously published research.


Asunto(s)
Hockey/lesiones , Adolescente , Traumatismos en Atletas/epidemiología , Traumatismos en Atletas/etiología , Conmoción Encefálica/etiología , Niño , Preescolar , Fracturas Óseas/etiología , Hockey/estadística & datos numéricos , Humanos , Incidencia , Luxaciones Articulares/etiología , Masculino , Ontario/epidemiología , Estudios Prospectivos , Esguinces y Distensiones/etiología
13.
Science ; 323(5911): 227, 2009 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-18974316

RESUMEN

White-nose syndrome (WNS) is a condition associated with an unprecedented bat mortality event in the northeastern United States. Since the winter of 2006*2007, bat declines exceeding 75% have been observed at surveyed hibernacula. Affected bats often present with visually striking white fungal growth on their muzzles, ears, and/or wing membranes. Direct microscopy and culture analyses demonstrated that the skin of WNS-affected bats is colonized by a psychrophilic fungus that is phylogenetically related to Geomyces spp. but with a conidial morphology distinct from characterized members of this genus. This report characterizes the cutaneous fungal infection associated with WNS.


Asunto(s)
Ascomicetos/clasificación , Ascomicetos/aislamiento & purificación , Quirópteros/microbiología , Dermatomicosis/veterinaria , Piel/microbiología , Animales , Ascomicetos/citología , Ascomicetos/genética , Quirópteros/fisiología , Frío , Enfermedades Transmisibles Emergentes/epidemiología , Enfermedades Transmisibles Emergentes/microbiología , Enfermedades Transmisibles Emergentes/patología , Enfermedades Transmisibles Emergentes/veterinaria , Dermatomicosis/epidemiología , Dermatomicosis/microbiología , Dermatomicosis/patología , Hibernación , New England/epidemiología , Onygenales/clasificación , Onygenales/citología , Onygenales/genética , Onygenales/crecimiento & desarrollo , Filogenia , Piel/patología , Esporas Fúngicas/citología
14.
Med Sci Sports Exerc ; 37(10): 1658-63, 2005 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-16260964

RESUMEN

PURPOSE: The purpose of this study was to determine injury rates in a youth ice hockey program over two seasons (2002-2004). Injury rates for age groups (4-18 yr) and for different levels of competition were compared. Another purpose was to determine the effect of body checking on injury rates among these youths. METHODS: A prospective injury report form was completed by a volunteer trainer for each injury that caused a loss of player time and resulted in evaluation by a physician. The injury form documented age group, type of injury, length of time that the player missed action due to the injury, location of the injury, and circumstances that led to the injury. Participants included 2632 boys aged 4-18 who played in the 2002-2003 season and 2639 boys who played in the 2003-2004 season. RESULTS: Injuries were four times more likely to occur in games than practices. Boys who played in the most advanced levels of competition are 6.1 times more likely to be injured than boys playing in house leagues. Injury rates during games showed a trend toward increasing with the age of the player. Injury rates spiked the first year that body checking was introduced in two different competition levels. Injury rates also spiked with the onset of adolescence (age 13). CONCLUSION: The study findings suggest that the introduction of body checking at age 9 to competitive youth hockey causes an immediate but relatively short-term increase in injury rates. The period of adjustment that accompanies body checking should be taken into account when determining the age at which body checking is introduced.


Asunto(s)
Hockey/lesiones , Adolescente , Niño , Preescolar , Hockey/estadística & datos numéricos , Humanos , Masculino , Estudios Prospectivos , Heridas y Lesiones/epidemiología
15.
Inorg Chem ; 42(20): 6564-74, 2003 Oct 06.
Artículo en Inglés | MEDLINE | ID: mdl-14514334

RESUMEN

The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays.

16.
Inorg Chem ; 41(20): 5255-68, 2002 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-12354060

RESUMEN

We have investigated the effect of complexation of different phosphorus ligands on the stability, solid state structure, and spectroscopic properties (NMR, IR, UV-vis) of a 5,15-diphenyl-substituted ruthenium porphyrin, (MeOH)Ru(II)(CO)(DPP) 2 [DPP = 5,15-bis(3',5'-di-tert-butyl)phenyl-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin]. The ligands used are PPh(3), diphenyl(phenylacetenyl)phosphine (DPAP), bis(diphenylphosphino)acetylene (DPPA), tris(phenylacetenyl)phosphine [(PA)(3)P], and diethyl (phenylacetenyl)phosphonite [PAP(OEt)(2)]. The mono-phosphine complexes (PR(3))Ru(II)(CO)(DPP) are readily formed in solution in quantitative yields. The complexes display association constants ranging from 1.2 x 10(4) M(-1) for PPh(3) to 4.8 x 10(6) M(-1) for PAP(OEt)(2). The weak association of PPh(3) does not correlate with its pK(a), delta((31)P), or cone angle value and is attributed to steric effects. Due to their kinetic lability, which is shown by 2D NMR spectroscopy, and the weakening of the carbonyl ligand via a trans effect, the mono-phosphine complexes could not be isolated. IR spectroscopy gives the relative order of pi-acceptor strength as PPh(3) < DPAP, DPPA < (PA)(3)P < PAP(OEt)(2), whereas the relative order of the sigma-donor strength is PPh(3) < (PA)(3)P < DPAP, DPPA < PAP(OEt)(2), based on the calculated pK(a) values and on the (31)P((1)H) NMR chemical shifts of the ligands. The chemical shift differences in the (31)P9(1)H)) NMR spectra upon ligand binding display a linear correlation with the calculated pK(a) values of the protonated ligands HPR(3)(+); we propose that the pK(a), and probably other electronic properties, of a specific phosphorus ligand can be estimated on the basis of the chemical shift difference Deltadelta((31)P) upon complexation to a metalloporphyrin. The bis-phosphine complexes can be isolated in pure form by crystallization from CHCl(3)-MeOH solutions using excess ligand. Association of the second ligand is in the same order of magnitude as the first binding for the phosphines, but the second phosphonite binding is decreased by a factor of about 100. The solid state structures show only marginal differences in the geometrical parameters. The calculated and the crystallographic cone angles of the ligands generally do not match, apart from the values obtained for PAP(OEt)(2).

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