No room for side‐on: In the complex shown, Et3SiH is bound to the cationic IrIII center in an unprecedented end‐on fashion through the SiH bond with no appreciable metal–silicon interaction (white H, green Si, pink Ir, red O, orange P, gray C). The long Ir⋅⋅⋅Si distance of 3.346(1) Å is 0.97 Å greater than the sum of the covalent radii of Ir and Si. DFT studies indicate that the tBu substituents on the bidentate phosphorus ligand dictate the coordination mode of the silane.
The cationic iridium pincer complex [(POCOP)Ir(H)(acetone)](+)[B(C(6)F(5))(4)](-) {1, POCOP = 2,6-[OP(tBu)(2)](2)C(6)H(3)} was found to be a highly active catalyst for the room-temperature cleavage and reduction of a wide variety of unactivated alkyl ethers including primary, secondary, and tertiary alkyl ethers as well as aryl alkyl ethers by triethylsilane. Mechanistic studies have revealed the full details of the catalytic cycle with the catalyst resting state(s) depending on the basicity of the alkyl ether. During the catalytic reduction of diethyl ether, cationic iridium silane complex, [(POCOP)Ir(H)(eta(1)-Et(3)SiH)](+)[B(C(6)F(5))(4)](-) (3), and Et(2)O are in rapid equilibrium with neutral dihydride, (POCOP)Ir(H)(2) (5) and diethyl(triethylsilyl)oxonium ion, [Et(3)SiOEt(2)](+)[B(C(6)F(5))(4)](-) (7), with 5 + 7 strongly favored. Species 7 has been isolated from the reaction mixture and fully characterized. The turnover-limiting step in this cycle is the reduction of 7 by the neutral dihydride 5. The relative rates of reduction of 7 by dihydride 5 and Et(3)SiH were determined to be approximately 30,000:1. In the cleavage of the less basic ethers anisole and EtOSiEt(3), the cationic iridium silane complex, 3, was found to be the catalyst resting state. The hydride reduction of the intermediate oxonium ion EtO(SiEt(3))(2)(+), 9, occurs via attack by Et(3)SiH. In the case of anisole, the intermediate PhMeOSiEt(3)(+), 10, is reduced by 5 and/or Et(3)SiH.
A highly active cationic Ir(III) hydride complex catalyzes the reduction of primary, secondary, and tertiary chlorides, bromides, and iodides as well as certain fluorides by Et3SiH. The catalytic cycle appears to operate by a unique process in which an electrophilic iridium silane complex acts as a silylating reagent to produce a silyl-substituted halonium ion which is then readily reduced by the nucleophilic dihydride formed following silyl transfer.
As an alternative approach against multidrug-resistant bacterial infections, phages are now being increasingly investigated as effective therapeutic agents. Here, aiming to design an efficient phage cocktail against Aeromonas salmonicida infections, we isolated and characterized five lytic A. salmonicida phages, AS-szw, AS-yj, AS-zj, AS-sw, and AS-gz. The results of morphological and genomic analysis suggested that all these phages are affiliated to the T4virus genus of the Caudovirales order. Their heterogeneous lytic capacities against A. salmonicida strains were demonstrated by experiments. A series of phage cocktails were prepared and investigated in vitro. We observed that the cocktail combining AS-gz and AS-yj showed significantly higher antimicrobial activity than other cocktails and individual phages. Given the divergent genomes between the phages AS-yj and AS-gz, our results highlight that the heterogeneous mechanisms that phages use to infect their hosts likely lead to phage synergy in killing the host. Conclusively, our study described a strategy to develop an effective and promising phage cocktail as a therapeutic agent to combat A. salmonicida infections, and thereby to control the outbreak of relevant fish diseases. Our study suggests that in vitro investigations into phages are prerequisite to obtain satisfying phage cocktails prior to application in practice.
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