Thermal treatment of the ReIII hydride complex [ReH­(η5-C6H7)­(η6-C6H6)]+ in CH3CN results in the formation of [Re­(η6-C6H6)­(NCCH3)3]+. This semi-solvated complex is remarkably stable under an ambient atmosphere and exhibits a fast CH3CN self-exchange, which facilitates substitution reactions. The CH3CN ligands are replaced by σ-donating phosphines such as trimethyl phosphine (PMe3), triphenyl phosphine (PPh3), or the bidentate 1,2-bis­(diphenylphosphino)­ethane (dppe) to afford [Re­(η6-C6H6)­(NCCH3)3–x (PR3) x ]+ (if R = Me, then x = 2; if R = Ph, then x = 1 or 2) or [Re­(η6-C6H6)­(dppe)­(NCCH3)]+, respectively. [Re­(η6-C6H6)­(NCCH3)3]+ also reacts with π-acceptors such as 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), or CO (1 atm) to give [Re­(η6-C6H6)­(L)­(NCCH3)]+ (L = bipy or phen) and [Re­(η6-C6H6)­(CO)­(NCCH3)2]+, respectively. The latter does not show any signs of decomposition after being exposed to an ambient atmosphere for multiple days. Additionally, [Re­(η6-C6H6)­(NCCH3)3]+ reacts with π-donors such as the dienes 2,3-dimethyl-1,3-butadiene (DMBD), norbornadiene (NBD), or 1,5-cyclooctadiene (COD) to give [Re­(η6-C6H6)­(η4-diene)­(NCCH3)]+ (diene = DMBD, NBD, and COD). All three complexes are extremely stable and do not decompose during purification by preparative high-performance liquid chromatography (aqueous acidic gradient). In the presence of 18-crown-6, [Re­(η6-C6H6)­(NCCH3)3]+ reacts with lithium cyclopentadienyl to give the sandwich complex [Re­(η5-C5H5)­(η6-C6H6)]. Loss of the coordinated benzene was observed when treating [Re­(η6-C6H6)­(NCCH3)3]+ with diphenylacetylene (PhCCPh), yielding the tetra-coordinated [Re­(NCCH3)­(η2-PhCCPh)3]+.

We introduce “The Integrator,” a novel technique to quantify transport and reaction metrics commonly used to characterize flow systems. This development consists of two products: (1) The Integrator sampling device and (2) its supporting mathematical framework, which is compatible with semi‐continuous sensor data. The use of The Integrator device simplifies the logistics of sample collection and greatly reduces the number of samples needed, making it ideal to characterize systems that are: (1) difficult to access, (2) large and thus intractable or highly heterogeneous, and (3) highly instrumented otherwise but where a more holistic, mechanistic understanding may be gained by monitoring one or more currently untracked elements. We tested and validated The Integrator technique using experimental data collected from a heart rate monitor (high‐quality, high‐frequency data in response to known excitation events) and solute tracer experiments conducted in two contrasting (fourth and seventh order) rivers. In the Supporting Information, we provide details concerning the design of The Integrator device used in our field case studies and provide insight into potential improvements. Despite our case studies focus on the analysis of conservative and reactive transport of solutes in rivers, the principles behind The Integrator technique can be used to monitor water quality in hyporheic zones, aquifers, wetlands, swamps, karsts, oceans, wastewater treatment plants, pipe networks, and air quality. Furthermore, special arrangements of Integrator devices can be used to gather data at spatial and temporal resolutions that are currently unattainable due to high transportation and/or personnel costs.

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