Boryl- and Silyl-Substituted Mixed Sandwich Compounds of Scandium.

An improved, one-pot synthesis of the linear sandwich compound [Sc(η5 -C5 H5 )(η8 -C8 H8 )] is presented. The synthetic procedure is amenable to boryl- and silyl-substituted cyclopentadienyl and cyclooctatetraenyl ligands, thereby yielding the first functionalized derivatives. We found that the synthesis of the silyl-substituted mixed sandwich complexes produces higher yields when the ligand exchange is carried out stepwise, by isolating the intermediate trimethylsilylated half-sandwich complex [Sc(η8 -C8 H7 SiMe3 )Cl(THF)] (THF=tetrahydrofuran). The molecular structures of the parent complex, as well as of its mono-boryl-substituted derivatives, have been determined by single-crystal X-ray diffraction. In addition, the optical and electrochemical properties of the mixed sandwich complexes are reported.

Does the Arthroscopic Latarjet Procedure Effectively Correct "Off-Track" Hill-Sachs Lesions?

BACKGROUND: The glenoid track concept describes the dynamic interaction of bipolar bone loss in anterior glenohumeral instability. Initial studies have successfully demonstrated this concept's application in clinical populations. In clinical practice, the Latarjet procedure is commonly the preferred treatment in addressing "off-track" Hill-Sachs lesions. The effectiveness of this procedure in restoring such lesions to an "on-track" state, however, has not yet been evaluated or described in the literature. HYPOTHESIS: The Latarjet procedure would transform "off-track" Hill-Sachs lesions to "on-track" lesions. Lesions would remain "on-track" during follow-up, despite glenoid remodeling. STUDY DESIGN: Case series; Level of evidence, 4. METHODS: Patients with "off-track" Hill-Sachs lesions treated with the arthroscopic Latarjet procedure between March 2013 and May 2014 were included. Glenoid track and coracoid graft contact surface area measurements using 3-dimensional computed tomography (3D-CT) were performed preoperatively and at 6-week, 6-month, and at least 12-month (final) follow-up. The mean final follow-up was 23 months. The glenoid diameter, as a percentage of the native glenoid, was also calculated from this imaging. RESULTS: Twenty-six patients met the inclusion criteria. 3D-CT scans were available for all patients preoperatively and postoperatively, with 21 patients (81%) undergoing 6-month follow-up CT and 19 patients (73%) undergoing final follow-up CT. Hill-Sachs lesions remained "on-track" at all follow-up time points. The mean glenoid diameter changed significantly from 84.6% preoperatively to 122.8% at 6 weeks ( P < .001) and from 120.5% at 6 months to 113.9% at final follow-up ( P = .005). This was also reflected in significant remodeling seen in the coracoid graft articular contact area (6 weeks to 6 months, P = .024; 6 months to final follow-up, P = .002). This persisting glenoid arc enlargement at final follow-up avoided "off-track" Hill-Sachs lesions in 6 of 19 patients (32%), which would otherwise have occurred had the coracoid graft remodeled to native glenoid dimensions. CONCLUSION: The Latarjet procedure provides an effective treatment for "off-track" engaging Hill-Sachs lesions, despite an evident glenoid remodeling process. At a mean of 23 months postoperatively, a mean persisting enlargement of the glenoid arc of 14% beyond native dimensions remained, avoiding a recurrent "off-track" lesion in 32% of patients, which would otherwise have occurred with complete remodeling.

Polymerization of 1-Phosphaisoprene: Synthesis and Characterization of a Chemically Functional Phosphorus Version of Natural Rubber.

Macromolecules derived from 1,3-dienes, such as polyisoprene (or natural rubber), are of considerable importance in polymer science. Given the parallels between P=C and C=C bonds, the prospect of polymerizing P-containing 1,3-dienes, such as 1-phosphaisoprene, is intriguing due to the unique chemical functionality imparted by the heavier element combined with their structural relationship to natural rubber. Herein, we report the synthesis, characterization and coordination chemistry of the first polymers derived from Mes*P=CR-CH=CH2 (Mes*=2,4,6-t-Bu3 C6 H2 ; R=H, Me). In the case of 1-phosphaisoprene (R=Me), the monomer is isolable and its anionic polymerization affords a polymer that retains P=C bonds in its microstructure. The chemical functionality of these novel materials is demonstrated by forming the macromolecular gold(I) complex where the P=C bond is retained for further chemical elaboration.

Surgical anatomy of medial open-wedge high tibial osteotomy: crucial steps and pitfalls.

PURPOSE: To give an overview of the basic knowledge of the functional surgical anatomy of the proximal lower leg and the popliteal region relevant to medial high tibial osteotomy (HTO) as key anatomical structures in spatial relation to the popliteal region and the proximal tibiofibular joint are usually not directly visible and thus escape a direct inspection. METHODS: The surgical anatomy of the human proximal lower leg and its relevance for HTO are illustrated with a special emphasis on the individual steps of the operation involving creation of the osteotomy planes and plate fixation. RESULTS: The posteriorly located popliteal neurovascular bundle, but also lateral structures such as the peroneal nerve, the head of the fibula and the lateral collateral ligament must be protected from the instruments used for osteotomy. Neither positioning the knee joint in flexion, nor the posterior thin muscle layer of the popliteal muscle offers adequate protection of the popliteal neurovascular bundle when performing the osteotomy. Tactile feedback through a loss-of-resistance when the opposite cortex is perforated is only possible when sawing and drilling is performed in a pounding fashion. Kirschner wires with a proximal thread, therefore, always need to be introduced under fluoroscopic control. Due to anatomy of the tibial head, the tibial slope may increase inadvertently. CONCLUSIONS: Enhanced surgical knowledge of anatomical structures that are at a potential risk during the different steps of osteotomy or plate fixation will help to avoid possible injuries. LEVEL OF EVIDENCE: Expert opinion, Level V.

Arthroscopic Repair of Subscapularis Tendon Tears.

The subscapularis is the largest and strongest muscle of the rotator cuff, and it plays an essential role in global shoulder function. Beyond its primary function as an internal rotator, the subscapularis also acts to pull the humeral head posteriorly on the glenoid and is an important dynamic and static anterior stabilizer of the glenohumeral joint. In comparison with tears of the tendons of the rest of the rotator cuff, isolated tears of the subscapularis have a tendency for both early retraction and fatty infiltration. Consequently, full-thickness tears of the subscapularis tendon generally require surgical management. Arthroscopic suture-anchor repair allows anatomic reconstruction of the anterior aspect of the rotator cuff, with all of the benefits of arthroscopic surgery. The principal steps of this procedure include (1) verifying the subscapularis tear and identifying any concomitant lesions during diagnostic arthroscopy, (2) exposing the subscapularis tendon, (3) releasing tendon adhesions and so enabling anatomic reduction, (4) placing suture anchors at the anatomic subscapularis footprint on the lesser tuberosity and anatomically repairing the subscapularis tendon to its anatomic insertion, and (5) performing biceps tenodesis or tenotomy, if indicated. Postoperatively, patients with an isolated subscapularis tear are managed with immobilization in a sling for 6 weeks, while those with combined anterosuperior rotator cuff tears are managed with an abduction pillow. Arthroscopic subscapularis reconstruction provides a good structural repair, substantially restores shoulder mobility and strength, reduces pain, and results in high levels of patient satisfaction and return of shoulder function as measured by functional outcome scores.

Ansa-Complexes of [Mn(η(5) -C5 H5 )(η(6) -C6 H6 )]: Preparation, Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3).

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa-bridging elements. Their preparation was achieved by salt-elimination reactions of the dilithiated precursor [Mn(η(5) -C5 H4 Li)(η(6) -C6 H5 Li)]⋅pmdta (pmdta=N,N,N',N',N''-pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single-atom-bridged derivatives, [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] and [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SiPh2 ], could also be determined by X-ray structural analysis. We investigated for the first time the reactivity of these ansa-cyclopentadienyl-benzene manganese compounds. The reaction of the distannyl-bridged complex [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )Sn2 tBu4 ] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn-Sn bond to give a triatomic ansa-bridge. The investigation of the ring-opening polymerization (ROP) capability of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] with [Pt(PEt3 )3 ] showed that an unexpected, unselective insertion into the Cipso -Sn bonds of [Mn(η(5) -C5 H4 )(η(6) -C6 H5 )SntBu2 ] had occurred.

Ansa-bridged bis(benzene) titanium complexes.

Taking advantage of an improved synthesis of [Ti(η(6) -C6 H6 )2 ], we report here the first examples of ansa-bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η(6) -C6 H6 )2 ] with nBuLi in the presence of N,N,N',N'',N''-pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1'-dilithio salt [Ti(η(6) -C6 H5 Li)2 ]⋅pmdta that enables the preparation of the first one- and two-atom-bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X-ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η(6) -C6 H6 )2 ] is found to react with the Lewis base 1,3-dimethylimidazole-2-ylidene (IMe) to give the bent sandwich complex [Ti(η(6) -C6 H6 )2 (IMe)].

f-Block Ansa Complexes in the Solid State: [3]Thoro- and [3]Uranocenophanes.

The preparation of [3]thoro- and [3]uranocenophanes, the first structurally authenticated ansa-bridged complexes of actinocenes, is reported. Following a flytrap route, 1,2-bis(cyclooctatetraenyldimethylsilyl)methane was synthesized, reduced to its tetraanion, and subsequently converted into bridged uranocene and thorocene complexes by salt metathesis with the corresponding actinide tetrachlorides. In addition, their electronic structures have been investigated by experimental (UV/Vis spectroscopy, cyclic voltammetry) and theoretical (DFT) methods.

A paramagnetic heterobimetallic polymer: synthesis, reactivity, and ring-opening polymerization of tin-bridged homo- and heteroleptic vanadoarenophanes.

The synthesis of the first tin-bridged bis(benzene) vanadium and trovacene sandwich compounds and the investigation of their oxidative addition and insertion behavior are reported. The vanadoarenophanes and the corresponding platinum insertion products were fully characterized including electrochemical and electron paramagnetic resonance (EPR) measurements. Controllable ring-opening polymerization of the heteroleptic tin-bridged [1]trovacenophane using Karstedt's catalyst yields a high molecular weight polymer (up to M(n) = 89 200 g·mol(-1)) composed of d(5)-vanadium metal centers in the main chain, making it a rare example of a spin-carrying macromolecule. Magnetic susceptibility measurements (SQUID) confirm the paramagnetic scaffold with repeating S = 1/2 centers in the main chain and suggest antiferromagnetic interactions between adjacent spin sites (Weiss constant Θ = -2.9 K).

Long-term results of arthroscopically assisted anatomical single-bundle anterior cruciate ligament reconstruction using patellar tendon autograft: are there any predictors for the development of osteoarthritis?

PURPOSE: The primary purpose of our study was to analyse the long-term outcome of patients treated for anterior cruciate ligament (ACL) tears by anatomical single-bundle ACL reconstruction with patellar tendon autograft. The secondary purpose was to identify predictive factors for good outcome and occurrence of osteoarthritis. METHODS: Sixty-three patients (m:f = 54:9; mean age at surgery, 27 ± 7 years) treated by ACL reconstruction were evaluated with a mean follow-up of 16 ± 1 years using IKDC2000, the SF36, Lysholm and Tegner score, Knee Society score, visual analogue scale for pain and satisfaction and KOOS. The femoral tunnel position was evaluated according to Sommer. It was also assessed in percentage of the Blumensaat line and the tibial tunnel position in percentage of the total anterior-posterior plateau length. The extent of osteoarthritis was graded according to the Kellgren-Lawrence score. RESULTS: The total IKDC2000 was normal in 20 (32 %), nearly normal in 29 (46 %), abnormal in 12 (19 %) and severely abnormal in 3 (5 %) of patients. The mean total SF-36 was 89 ± 13, the Lysholm score 95 ± 12, the Knee Society score 191 ± 16 and the total KOOS 84 ± 19. The Tegner score decreased from pre-injury 7(4-10) to 6 (2-10) at follow-up. The Kellgren-Lawrence score was normal in 17 (27 %), suspected osteoarthritis in 25 (40 %), minimal osteoarthritis in 5 (8 %), moderate osteoarthritis in 9 (14 %) and severe osteoarthritis in 3 patients (5 %). The femoral tunnel was in zone A in 43 patients (68 %), in zone B in 16 (25 %) and in zone C in 4 patients (7 %). The femoral tunnel position in percentage of the Blumensaat line was 49 ± 3 (range, 44-57), and the tibial tunnel position in percentage of the total anterior-posterior plateau length was 32 ± 6 (range, 21-46). Patients with meniscal lesion at the time of ACL tear showed significantly less favourable outcomes than those without. CONCLUSIONS: Patients treated by the proposed ACL reconstruction technique showed on average good to excellent long-term results. A meniscal lesion at the time of ACL tear was highly predictive for less favourable outcome.

Heteroleptic [n]chromoarenophanes: ansa complexes derived from [Cr(η(5)-C5H5)(η(6)-C6H6)].

The synthesis of ansa complexes has been studied intensively owing to their importance as homogeneous catalysts and as precursors of metal-containing polymers. However, paramagnetic non-metallocene derivatives are rare and have been limited to examples with vanadium and titanium. Herein, we report an efficient procedure for the selective dilithiation of paramagnetic sandwich complex [Cr(η(5)-C(5)H(5))(η(6)-C(6)H(6))], which allows the preparation of a series of [n]chromoarenophanes (n = 1, 2, 3) that feature silicon, germanium, and tin atoms at the bridging positions. The electronic and structural properties of these complexes were probed by X-ray diffraction analysis, cyclic voltammetry, and by UV/Vis and EPR spectroscopy. The spectroscopic parameters for the strained and less strained complexes (i.e., with multiple-atom linkers) indicate that the unpaired electron resides primarily in a d(z)2 orbital on chromium(I); this result was also supported by density functional theory (DFT) calculations. We did not observe a correlation between the experimental UV/Vis and EPR data and the degree of molecular distortion in these ansa complexes. The treatment of tin-bridged complex [Cr(η(5)-C(5)H(4))(η(6)-C(6)H(5))SntBu(2)] with [Pt(PEt(3))(3)] results in the non-regioselective insertion of the low-valent Pt(0) fragment into the C(ipso)-Sn bonds in both the five- and six-membered rings, thereby furnishing a bimetallic complex. This observed reactivity suggests that ansa complexes of this type are promising starting materials for the synthesis of bimetallic complexes in general and also underline their potential to undergo ring-opening processes to yield new metal-containing polymers.

A clinical sign to detect root avulsions of the posterior horn of the medial meniscus.

PURPOSE: The goal of the present report was to describe a new clinical sign to make a clinical diagnosis of meniscal extrusion related to medial meniscal root avulsion. METHODS: Description of an easy clinical sign to detect extrusion of the medial meniscus at the anteromedial joint line. A varus stress test was applied in full extension before and after transosseous repair of an isolated traumatic avulsion of the posterior root of the medial meniscus in a 21-year-old patient. The clinical sign was verified by sectioning of the meniscotibial ligament during knee arthroplasty surgery in 3 patients. RESULTS: With a deficient posterior root, the clinical sign was positive, showing anteromedial extrusion under varus stress. After repair and at clinical follow-up, extrusion was normalized. CONCLUSION: Making the clinical diagnosis of medial meniscus extrusion after knee injury by applying a simple varus stress test to the knee and palpating the anteromedial meniscal extrusion might help physicians to suspect a medial meniscus root tear in the early stages after the injury as well as to evaluate its reduction after repair. A varus stress test in full extension should be performed systematically in patients where a root tear of the medial meniscus is suspected as well as after surgery to evaluate the success of the repair.