Triphosphiranes as phosphinidene-transfer agents - synthesis of regular and chelating NHC phosphinidene adducts.

In this contribution we describe the general use of aryl-substituted triphosphiranes (Ar3P3; Ar = Mes, Dip, Tip) as phosphinidene transfer reagents towards N-heterocyclic carbenes (NHCs) to give a library of twelve N-heterocyclic carbene phosphinidene adducts of the type ArPNHC (NHCPs), in which the NHCs have varying steric profiles, allowing a systematic evaluation of their structural and NMR-spectroscopic properties. In the next series of experiments we utilized 1,3- and 1,4-phenylene bridged bis-NHCs to access a new class of chelating bis(NHCP)s, of which three derivatives could be structurally characterized. The 1,4-phenylene derivatives were shown to be susceptible to P-CNHC bond cleavage when irradiated with an LED (396 nm), providing a rare example of phosphinidene release from NHCPs. The coordination chemistry of 1,3-phenylene bridged bis(NHCP)s towards GeCl2(dioxane) and GaI3 was investigated and revealed the formation of ion-separated cationic complexes, with significant charge transfer from the ligand to the metal center according to NBO analyses.

Phosphine-catalysed reductive coupling of dihalophosphanes.

Classically tetraaryl diphosphanes have been synthesized through Wurtz-type reductive coupling of halophosphanes R2PX or more recently, through the dehydrocoupling of phosphines R2PH. Catalytic variants of the dehydrocoupling reaction have been reported, but are limited to R2PH compounds. Using PEt3 as a catalyst, we now show that TipPBr2 (Tip = 2,4,6-iPr3C6H2) is selectively coupled to give the dibromodiphosphane (TipPBr)2 (1), a compound not accessible using classic Mg reduction. Surprisingly, when using DipPBr2 (Dip = 2,6-iPr3C6H3) in the PEt3 catalysed reductive coupling the diphosphene (PDip)2 (2) with a PP double was formed selectively. In benzene solutions (PDip)2 has a half life time of ca. 28 days and can be utilized with NHCs to access NHC-phosphinidene adducts. To show that this protocol is more widely applicable, we show that Ph2PCl and Mes2PX (X = Cl, Br) are efficiently coupled using 10 mol% of PEt3 to give (Ph2P)2 and (Mes2P)2, respectively. Control experiments show that [BrPEt3]Br is a potential oxidation product in the catalytic cycle, which can be debrominated by Zn dust as a sacrificial reductant.

Aryl-substituted triarsiranes: synthesis and reactivity.

Cyclotriarsanes are rare and described herein is a scalable synthetic protocol towards (AsAr)3, which allowed to study their reactivity towards [Cp2Ti(C2(SiMe3)2)], affording titanocene diarsene complexes, and towards N-heterocyclic carbenes (NHCs) to give straightforward access to a variety of NHC-arsinidene adducts.

To defer or not to defer? A German longitudinal multicentric assessment of clinical practice in urology during the COVID-19 pandemic.

INTRODUCTION: After the outbreak of COVID-19 unprecedented changes in the healthcare systems worldwide were necessary resulting in a reduction of urological capacities with postponements of consultations and surgeries. MATERIAL AND METHODS: An email was sent to 66 urological hospitals with focus on robotic surgery (RS) including a link to a questionnaire (e.g. bed/staff capacity, surgical caseload, protection measures during RS) that covered three time points: a representative baseline week prior to COVID-19, the week of March 16th-22nd and April 20th-26th 2020. The results were evaluated using descriptive analyses. RESULTS: 27 out of 66 questionnaires were analyzed (response rate: 41%). We found a decrease of 11% in hospital beds and 25% in OR capacity with equal reductions for endourological, open and robotic procedures. Primary surgical treatment of urolithiasis and benign prostate syndrome (BPS) but also of testicular and penile cancer dropped by at least 50% while the decrease of surgeries for prostate, renal and urothelial cancer (TUR-B and cystectomies) ranged from 15 to 37%. The use of personal protection equipment (PPE), screening of staff and patients and protection during RS was unevenly distributed in the different centers-however, the number of COVID-19 patients and urologists did not reach double digits. CONCLUSION: The German urological landscape has changed since the outbreak of COVID-19 with a significant shift of high priority surgeries but also continuation of elective surgical treatments. While screening and staff protection is employed heterogeneously, the number of infected German urologists stays low.

Terphenyl(bisamino)phosphines: electron-rich ligands for gold-catalysis.

Terphenyl(bisamino)phosphines have been identified as effective ligands in cationic gold(i) complexes for the hydroamination of acetylenes. These systems are related to Buchwald phosphines and their steric properties have been evaluated. Effective hydroamination was noted even at low catalyst loadings and a series of cationic gold(i) complexes has been structurally characterized clearly indicating stabilizing effects through gold-arene interactions.

Complications of the urinary incontinence system ATOMS: description of risk factors and how to prevent these pitfalls.

BACKGROUND: We report on our multicentre evaluation of the occurrence and management of complications with the ATOMS device (A.M.I., Austria). PATIENTS AND METHODS: Between 10/09 and 09/18, a total of 187 patients with persistent postoperative stress urinary incontinence received an ATOMS device in Madrid (n = 101) or Halle (n = 86). This prospective evaluation was carried out consecutively. In addition to complications, patient age, BMI, comorbidities and previous treatments for prostate cancer and urinary incontinence were examined. Statistical analysis was performed with GraphPad Prism 7® (GraphPad Software, Inc., La Jolla, USA); p < 0.05 was considered significant. RESULTS: The average age of the overall population was 69.4 years, with a mean CCI of 4.3. In total, 18.2% of the patients had diabetes mellitus, 21.9% were irradiated, and 14.1% and 22.9% underwent previous surgery for urinary incontinence and urethral stricture, respectively. The overall success rate of the device was 80.2%. A total of 51 postoperative complications (51/187, 27.3%) were observed, with 18 grade I (9.6%), 1 grade II (0.5%), 3 grade IIIa (1.6%) and 29 grade IIIb (15.5%) complications. The most serious postoperative complications were primary wound infection (8/187, 4.3%) and long-term cutaneous erosion with subsequent infection (15/187, 8.02%). The main risk factors for complications were previous radiotherapy (p = 0.003) and surgery for urethral stricture (p = 0.017). No other parameters were significant in bivariate analysis (p > 0.05). CONCLUSION: The most severe complications of ATOMS implantation were primary wound infection and cutaneous erosion, especially in the presence of previous radiotherapy. Particular focus on performing hygienic and accurate implantation techniques is recommended.

Minimally invasive robotic versus conventional open living donor kidney transplantation.

PURPOSE: First robotic-assisted kidney transplants (RAKT) were performed in Germany in 2016. To introduce and establish this method as a routine procedure for patients in transplantation medicine, our 2-year experiences are presented. METHODS: Non-randomized open-label cohort study to compare functional and operative results as well as complication rates between RAKT and standard open transplantation. Collected data are part of ERUS RAKT Group Registry. RESULTS: Since initiation of the RAKT program 21/27 transplantations after living kidney donations have been performed as RAKT. This represents the largest series of RAKT in Germany. Patient survival, transplant survival, and primary function rate are 100% (mean follow-up 12.9 ± 8.6 month). Mean incision to closure time was 306.1 ± 45.5, mean handling time 70.8 ± 13.1 min compared to 212.1 ± 40.6 min and 51.7 ± 9.9 min, respectively, in the standard group. Despite extended operating times using the robotic approach, comparable complication rates and graft function with significant reduction in median length of hospital stay (14 vs. 20 days) were observed. CONCLUSIONS: RAKT extends the options for recipients towards minimally invasive techniques. Compared to classic open surgery, RAKT appears to be safe in selected patients without influencing graft outcome or higher complication rates. However, RAKT till today is not suitable for all patients but seems to be one of the upcoming new standard techniques in kidney transplantation.

A selective route to aryl-triphosphiranes and their titanocene-induced fragmentation.

Triphosphiranes are three-membered phosphorus cycles and their fundamental reactivity has been studied in recent decades. We recently developed a high-yielding, selective synthesis for various aryl-substituted triphosphiranes. Variation of the reaction conditions in combination with theoretical studies helped to rationalize the formation of these homoleptic phosphorus ring systems and highly reactive intermediates could be isolated. In addition we showed that a titanocene synthon [Cp2Ti(btmsa)] facilitates the selective conversion of these triphosphiranes into titanocene diphosphene complexes. This unexpected reactivity mode was further studied theoretically and experimental evidence is presented for the proposed reaction mechanism.

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald-Hartwig Aminations.

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII -NHO complexes have been formed and their use as pre-catalysts in Buchwald-Hartwig aminations was explored. The most active system for catalytic C-N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.

An overview of the ATOMS generations: port types, functionality and risk factors.

BACKGROUND: We report the multicentre comparison of the different port types of the adjustable transobturator male incontinence system (ATOMS, A.M.I., Austria). METHODS: Between 10/09 and 10/16, 383 patients received an ATOMS. Of these, 63% received the inguinal port (IP, 2009-2013), 23% the intraoperative manually connectable scrotal port (SP, 2013-2015), and 14% the pre-connected fully silicone-covered scrotal port (SSP, 2014-2016). During the follow-up period, continence parameters, pain and quality of life ratings and postoperative port-associated complications were evaluated and compared. Statistical analysis was performed with GraphPad Prism 7®, p < 0.05 considered as significant. RESULTS: Regarding preoperative parameters (BMI, ASA score, previous radiotherapy/incontinence surgery, and preoperative 24-h pad count/24-h pad test), no significant differences were found. Regarding perioperative parameters, the mean operative time was significantly shorter for the SP and SSP (IP vs. SP p < 0.0001, IP vs. SSP p = 0.0048, SP vs. SSP p = 0.697). Comparison of the postoperative 24-h pad count, 24-h pad test and uroflowmetry data revealed no significant differences. However, the postoperative ICIQ-SF score was significantly better for the SSP (p = 0.0232) than the SP. A significant difference was also observed in postoperative port-associated complications. According to the Clavien-Dindo classification, we identified one grade I and 29 grade IIIb complications for the IP, 1 grade I and 6 grade IIIb complications for the SP, but only 2 grade IIIb complications for the SSP (IP vs. SP p = 0.0231, IP vs. SSP p = 0.0189 and SP vs. SSP p = 0.0453). CONCLUSION: The SSP shows fewer complications while retaining comparable efficacy.

Five-year experience with the adjustable transobturator male system for the treatment of male stress urinary incontinence: a single-center evaluation.

BACKGROUND: We report on our 5-year experience with the adjustable transobturator male system (ATOMS®, A.M.I., Feldkirch, Austria). METHODS: Between 10-2009 and 10-2014, 54 patients received an ATOMS. The mean follow-up of this retrospective observational trial was 27.5 ± 18.4 (2.3-59) months. Within each follow-up, the following were evaluated: micturition protocol, 24-h pad count, uroflowmetry and residual volume. Statistical analysis was performed with SigmaPlot® 11.0, p < 0.05 considered as significant. RESULTS: Stress urinary incontinence (SUI) I°, II° and III° was seen in 1 (1.9 %), 16 (29.6 %) and 37 patients (68.5 %), respectively. In summary, 48.1 % of the patients became "dry" (0-"safty pad"/day), while 29.6 % achieved at least an "improvement" of about more than 50 % (1-2 pads/day), which corresponds to an overall success rate of 77.7 %. The mean number of pads/day decreased from 7.7 to 1.6. Regarding the initial degree of SUI, patients with mild or moderate incontinence had a significantly better outcome (p = 0.002, 95 % CI 0.9066 to 2.760). Postoperative complications were scaled according to the Clavien classification, in which we have seen 4 grade I-, 1 grade IIIa- and 9 grade IIIb-complications (overall 25.9 %). The evaluation of quality of life by ICIQ-SF showed a significant improvement (p = 0.0001, 95 % CI -14.56 to -11.75). CONCLUSION: The treatment of male SUI using the ATOMS incontinence system achieved the best results in patients with mild and moderate incontinence. For severe incontinent patients, the system represents an efficient alternative.

Laparoendoscopic single-site versus conventional laparoscopic radical nephrectomy for renal cell cancer in patients with increased comorbidities and previous abdominal surgery: preliminary results of a single-centre retrospective study.

OBJECTIVE: Laparoendoscopic single-site surgery (LESS) represents an evolution of laparoscopy for the treatment for urologic diseases. The aim of this study is to investigate the feasibility of LESS in patients with increased comorbidities and previous abdominal surgery undergoing radical nephrectomy (LESS-RN) for renal cell carcinoma. MATERIALS AND METHODS: A total of 25 patients with increased comorbidities and previous abdominal surgery who underwent LESS-RN were compared to 31 patients with the same characteristics after conventional laparoscopic radical nephrectomy (LRN). LRN was performed between January 2009 and May 2010, and LESS-RNs were performed between June 2010 and November 2011. Demographic data and perioperative and postoperative variables were recorded and analysed. RESULTS: The mean ASA score in the LESS-RN and LRN groups was 3.2 ± 0.4, and the mean BMI was 32.7 ± 2.1 and 34.2 ± 0.8 kg/m(2), respectively. The mean operative time in the LESS-RN and LRN groups was 143.7 ± 24.3 and 130.6 ± 26.5 min, (p = 0.11), and the mean hospital stay was 3.8 ± 0.8 versus 4.2 ± 1.4 days in the two groups (p = 0.06), respectively. Three and four complications were recorded in the LESS-RN and in the LRN groups, for a mean complication rate of 12 and 12.9 % (p = 0.12), respectively All tumours were organ-confined with negative surgical margins, and the mean R.E.N.A.L nephrometry score for LESS-RN and LRN was 9.78 ± 1.7 and 9.82 ± 1.3 (p = 0.14), respectively. CONCLUSIONS: LESS-RN in patients with increased comorbidities and previous abdominal surgery is equally effective as LRN without compromising on surgical, oncologic short-term and postoperative outcomes.