Unraveling the Mechanism of 1,3-Diyne Cross-Metathesis Catalyzed by Silanolate-Supported Tungsten Alkylidyne Complexes.

The benzylidyne complex [PhC≡W{OSi(OtBu)3 }3 ] (1) catalyzed the cross-metathesis between 1,4-bis(trimethylsilyl)-1,3-butadiyne (2) and symmetrical 1,3-diynes (3) efficiently, which gave access to TMS-capped 1,3-diynes RC≡C-C≡CSiMe3 (4). Diyne cross-metathesis (DYCM) studies with 13 C-labeled diyne PhC≡13 C-13 C≡CPh (3*) revealed that this reaction proceeds through reversible carbon-carbon triple-bond cleavage and formation according to the conventional mechanism of alkyne metathesis. The reaction between 1 and 3* afforded the 3-phenylpropynylidyne complex PhC≡13 C-13 C≡W{OSi(OtBu)3 }3 ] (5*), indicating that alkynylalkylidyne complexes are likely to act as catalytically active species. Attempts to isolate 5* from mixtures of 1 and 3* afforded crystals of the ditungsten 2-butyne-1,4-diylidyne complex [(tBuO)3 SiO}3 W≡13 C-13 C≡13 C-13 C≡W{OSi(OtBu)3 }3 ] (6*), which was additionally characterized by X-ray diffraction analysis. Depolymerization-macrocyclization of a carbazole-butadiyne polymer, obtained from 3,6-diethynyl-9-dodecylcarbazole (7) under copper-catalyzed Hay coupling conditions, was also efficiently catalyzed by 1 and afforded a mixture of mono-, diyne- and triyne-containing tetrameric macrocycles, revealing that diyne disproportionation into monoynes and triynes occurs as a slow side reaction that interferes with a high diyne metathesis selectivity. Potential catalytic pathways were studied by means of quantum-chemical calculations, and kinetic studies were performed to substantiate an α,α-mechanism for the catalytic diyne metathesis reaction, which involves intermediate alkynylalkylidyne and α,α'-dialkynylmetallacyclobutadiene intermediates.

Impact of a Long Run on Injury-Related Biomechanics with Relation to Weekly Mileage in Trained Male Runners.

The purposes of this study were to compare selected biomechanical variables before and after a long run, and to assess the relationship between weekly running volume and changes in lower limb biomechanics after the run. Twelve trained habitual rearfoot strike male runners ran overground before and after a treadmill long run while kinematic and kinetic data were recorded. Repeated measures analysis of variance and Cohen's d effect sizes were used to compare kinematic and kinetic variables before and after the run. Loading rate was 6% higher after the run (p < .05) but this difference had a small effect size (d = .32). Moderate effects were found for a 25% increase in peak ankle eversion (d = 0.62) and a 10% increase in hip adduction (d = 0.60) after the run. These findings suggest that the completion of a submaximal long run does not yield potentially injurious lower limb biomechanics in uninjured rearfoot strike runners. Weekly running mileage was not correlated to biomechanical changes observed before and after the long run. Since biomechanical responses to the long run varied among runners, differences in other factors such as specific training regimens and neuromuscular control should be considered in future studies.

Joint stiffness and running economy during imposed forefoot strike before and after a long run in rearfoot strike runners.

Research has focused on the effects of acute strike pattern modifications on lower extremity joint stiffness and running economy (RE). Strike pattern modifications on running biomechanics have mostly been studied while runners complete short running bouts. This study examined the effects of an imposed forefoot strike (FFS) on RE and ankle and knee joint stiffness before and after a long run in habitual rearfoot strike (RFS) runners. Joint kinetics and RE were collected before and after a long run. Sagittal joint kinetics were computed from kinematic and ground reaction force data that were collected during over-ground running trials in 13 male runners. RE was measured during treadmill running. Knee flexion range of motion, knee extensor moment and ankle joint stiffness were lower while plantarflexor moment and knee joint stiffness were greater during imposed FFS compared with RFS. The long run did not influence the difference in ankle and knee joint stiffness between strike patterns. Runners were more economical during RFS than imposed FFS and RE was not influenced by the long run. These findings suggest that using a FFS pattern towards the end of a long run may not be mechanically or metabolically beneficial for well-trained male RFS runners.

Comparison of ankle kinematics and ground reaction forces between prospectively injured and uninjured collegiate cross country runners.

Biomechanical comparative studies on running-related injuries have included either currently or retrospectively injured runners. The purpose of this study was to prospectively compare ankle joint and ground reaction force variables between collegiate runners who developed injuries during the cross country season and those who did not. Running gait analyses using a motion capture system and force platform were conducted on 19 collegiate runners prior to the start of their cross country season. Ten runners sustained running-related injuries and 9 remained healthy during the course of the season. Strike index, peak loading rate of the vertical ground reaction force, dorsiflexion range of motion (ROM), eversion ROM, peak eversion angle, peak eversion velocity, and eversion duration from the start of the season were compared between injury groups. Ankle eversion ROM and peak eversion velocity were greater in uninjured runners while peak eversion angle was greater in injured runners. Greater ankle eversion ROM and eversion velocity with lower peak eversion angle may be beneficial in reducing injury risk in collegiate runners. The current data may only be applicable to collegiate cross country runners with similar training and racing schedules and threshold magnitudes of ankle kinematic variables to predict injury risk are still unknown.

Lower Limb Kinematics and Metabolic Cost During Elliptical Exercises and Treadmill Running.

The purpose of this study was to compare knee and hip joint kinematics previously associated with anterior knee pain and metabolic cost among conditions including treadmill running (TR), standard elliptical (SE), and lateral elliptical (LE) in healthy runners. Joint kinematics and metabolic parameters of 16 runners were collected during all 3 modalities using motion capture and a metabolic system, respectively. Sagittal knee range of motion (ROM) was greater in LE (P < .001) and SE (P < .001) compared with TR. Frontal and transverse plane hip ROM were greater in LE compared with SE (P < .001) and TR (P < .001). Contralateral pelvic drop ROM was smaller in SE compared with TR (P = .002) and LE (P = .005). Similar oxygen consumption was found during LE and TR (P = .39), but LE (P < .001) and TR (P < .001) required greater oxygen consumption than SE. Although LE yields similar metabolic cost to TR and produces hip kinematics that may help strengthen hip abductors, greater knee flexion and abduction during LE may increase symptoms in runners with anterior knee pain. The findings suggest that research on the implications of elliptical exercise for injured runners is needed.

Ankle and knee kinetics between strike patterns at common training speeds in competitive male runners.

The purpose of this study was to investigate the interaction of foot strike and common speeds on sagittal plane ankle and knee joint kinetics in competitive rear foot strike (RFS) runners when running with a RFS pattern and an imposed forefoot strike (FFS) pattern. Sixteen competitive habitual male RFS runners ran at two different speeds (i.e. 8 and 6 min mile(-1)) using their habitual RFS and an imposed FFS pattern. A repeated measures analysis of variance was used to assess a potential interaction between strike pattern and speed for selected ground reaction force (GRF) variables and, sagittal plane ankle and knee kinematic and kinetic variables. No foot strike and speed interaction was observed for any of the kinetic variables. Habitual RFS yielded a greater loading rate of the vertical GRF, peak ankle dorsiflexor moment, peak knee extensor moment, peak knee eccentric extensor power, peak dorsiflexion and sagittal plane knee range of motion compared to imposed FFS. Imposed FFS yielded greater maximum vertical GRF, peak ankle plantarflexor moment, peak ankle eccentric plantarflexor power and sagittal plane ankle ROM compared to habitual RFS. Consistent with previous literature, imposed FFS in habitual RFS reduces eccentric knee extensor and ankle dorsiflexor involvement but produce greater eccentric ankle plantarflexor action compared to RFS. These acute differences between strike patterns were independent of running speeds equivalent to typical easy and hard training runs in competitive male runners. Current findings along with previous literature suggest differences in lower extremity kinetics between habitual RFS and imposed FFS running are consistent among a variety of runner populations.

Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application.

Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity.