High level electronic structure calculations were used to evaluate reliable, self-consistent thermochemical data sets for the third row transition metal hexafluorides. The electron affinities, heats of formation, first (MF(6) --> MF(5) + F) and average M-F bond dissociation energies, and fluoride affinities of MF(6) (MF(6) + F(-) --> MF(7)(-)) and MF(5) (MF(5) + F(-) --> MF(6)(-)) were calculated. The electron affinities which are a direct measure for the oxidizer strength increase monotonically from WF(6) to AuF(6), with PtF(6) and AuF(6) being extremely powerful oxidizers. The inclusion of spin orbit corrections is necessary to obtain the correct qualitative order for the electron affinities. The calculated electron affinities increase with increasing atomic number, are in good agreement with the available experimental values, and are as follows: WF(6) (3.15 eV), ReF(6) (4.58 eV), OsF(6) (5.92 eV), IrF(6) (5.99 eV), PtF(6) (7.09 eV), and AuF(6) (8.20 eV). A wide range of density functional theory exchange-correlation functionals were also evaluated, and only three gave satisfactory results. The corresponding pentafluorides are extremely strong Lewis acids, with OsF(5), IrF(5), PtF(5), and AuF(5) significantly exceeding the acidity of SbF(5). The optimized geometries of the corresponding MF(7)(-) anions for W through Ir are classical MF(7)(-) anions with M-F bonds; however, for PtF(7)(-) and AuF(7)(-) non-classical anions were found with a very weak external F-F bond between an MF(6)(-) fragment and a fluorine atom. These two anions are text book examples for "superhalogens" and can serve as F atom sources under very mild conditions, explaining the ability of PtF(6) to convert NF(3) to NF(4)(+), ClF(5) to ClF(6)(+), and Xe to XeF(+) and why Bartlett failed to observe XePtF(6) as the reaction product of the PtF(6)/Xe reaction.
Introduction: Transposed brachiobasilic AV fistulas (BVT) have increasingly been performed in two stages. Published reports give conflicting results, perhaps in part as many reports of staged procedures eliminate those patients who “fail” the first stage (i.e. are lost to follow-up in addition to anatomic failure). Methods: A prospectively maintained database was reviewed to identify all patients at two institutions who underwent the first stage of planned two-stage BVT by the senior author. Success in this context was defined as patients who eventually underwent second stage fistula creation, leaving the operating room after the second stage with a patent, transposed fistula. Results: From October 2012 to June 2020, 218 patients underwent first-stage procedures. At the first visit, 185 (85%) of fistulas were patent, 23 (11%) were occluded, 8 (4%) of patients were lost to follow-up, and 2 (1%) died. In the interval before the second operation, another eight (4%) patients were lost to follow-up, two were cancelled for medical reasons, and two declined surgery, leaving a total of 173 patients who made it to the second stage (80%). At operation, four patients were found to have unusable veins, leaving a total of 169 patients who completed both stages. If all patients who underwent first stage are included, 77% of patients entering this pathway left the OR after their second stage with patent access. If those lost to follow-up are excluded, this number increases to 84%, while if all those lost to follow-up are assumed to mature, success increases to 85%. Conclusions: Depending on results in patients lost to follow-up, between 77% and 85% of patients undergoing first stage brachiobasilic fistulae undergo successful second stage transposition. These numbers are equivalent or slightly lower than published maturation rates for single-stage BVT, so there is little margin for failure at the second stage.
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