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1. A Hydride Migration Mechanism for the Mo‐Catalyzed Z ‐2‐Selective Isomerization of Terminal Alkenes

   https://doi.org/10.1002/cctc.202301052  

   Jenny, Sarah_E; Serviano, Juan_M; Nova, Ainara; Dobereiner, Graham_E (November 2023, ChemCatChem)

   Abstract The catalytic one‐bond isomerization (transposition) of 1‐alkenes is an emerging approach toZ‐2‐alkenes. Design of more selective catalysts would benefit from a mechanistic understanding of factors controllingZselectivity. We propose here a reaction pathway forcis‐Mo(CO)₄(PCy₃)(piperidine) (3), a precatalyst that shows highZselectivity for transposition of alpha olefins (e. g., 1‐octene to 2‐octene, 18 : 1Z : Eat 74 % conversion). Computational modeling of reaction pathways and isotopic labeling suggests the isomerization takes place via an allyl (1,3‐hydride shift) pathway, where oxidative addition offac‐(CO)₃Mo(PCy₃)(η²‐alkene) is followed by hydride migration from one position (cisto allyl C³carbon) to another (cisto allyl C¹carbon) via hydride/CO exchanges. Calculated barriers for the hydride migration pathway are lower than explored alternative mechanisms (e. g., change of allyl hapticity, allyl rotation). To our knowledge, this is the first study to propose such a hydride migration in alkene isomerization. 

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2. Bench‐Stable Dinuclear Mn(I) Catalysts in E ‐Selective Alkyne Semihydrogenation: A Mechanistic Investigation**

   https://doi.org/10.1002/chem.202201766  

   Abhyankar, Preshit_C; MacMillan, Samantha_N; Lacy, David_C (July 2022, Chemistry – A European Journal)

   Abstract Dinuclear manganese hydride complexes of the form [Mn₂(CO)₈(μ‐H)(μ‐PR₂)] (R=Ph,1; R=iPr,2) were used inE‐selective alkyne semi‐hydrogenation (E‐SASH) catalysis. Catalyst speciation studies revealed rich coordination chemistry and the complexes thus formed were isolated and in turn tested as catalysts; the results underscore the importance of dinuclearity in engendering the observedE‐selectivity and provide insights into the nature of the active catalyst. The insertion product obtained from treating2with (cyclopropylethynyl)benzene contains acis‐alkenyl bridging ligand with the cyclopropyl ring being intact. Treatment of this complex with H₂affords exclusivelytrans‐(2‐cyclopropylvinyl)benzene. These results, in addition to other control experiments, indicate a non‐radical mechanism forE‐SASH, which is highly unusual for Mn−H catalysts. The catalytically active species are virtually inactive towardscistotransalkene isomerization indicating that theE‐selective process is intrinsic and dinuclear complexes play a critical role. A reaction mechanism is proposed accounting for the observed reactivity which is fully consistent with a kinetic analysis of the rate limiting step and is further supported by DFT computations. 

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3. Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe ₃ ) ₂ , O t Bu) with an Iridium Hydride

   https://doi.org/10.1002/chem.202301863  

   Saint‐Denis, Tyler_G; Zhang, Bowen; Settineri, Nicholas_S; Handford, Rex_C; Hall, Michael_B; Tilley, T_Don (July 2023, Chemistry – A European Journal)

   Abstract Reactions of the Ir^Vhydride [^MeBDI^Dipp]IrH₄{BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐iPr₂C₆H₃} with E[N(SiMe₃)₂]₂(E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([^MeBDI^Dipp]IrH)₂(μ₂‐E)₂in good yields. Moreover, ([^MeBDI^Dipp]IrH)₂(μ₂‐Ge)₂was formed in situ from thermal decomposition of [^MeBDI^Dipp]Ir(H)₂Ge[N(SiMe₃)₂]₂. These reactions are accompanied by liberation of HN(SiMe₃)₂and H₂through the apparent cleavage of an E−N(SiMe₃)₂bond by Ir−H. In a reversal of this process, ([^MeBDI^Dipp]IrH)₂(μ₂‐E)₂reacted with excess H₂to regenerate [^MeBDI^Dipp]IrH₄. Varying the concentrations of reactants led to formation of the trimeric ([^MeBDI^Dipp]IrH₂)₃(μ₂‐E)₃. The further scope of this synthetic route was investigated with group 15 amides, and ([^MeBDI^Dipp]IrH)₂(μ₂‐Bi)₂was prepared by the reaction of [^MeBDI^Dipp]IrH₄with Bi(NMe₂)₃or Bi(OtBu)₃to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir₂E₂(E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir₂Bi₂is characterized as having a closed‐shell singlet ground state. 

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4. Aluminum‐Ligand Cooperative O−H Bond Activation Initiates Catalytic Transfer Hydrogenation

   https://doi.org/10.1002/cctc.202101869  

   Carr, Cody_R; Vesto, James_I; Xing, Xiujing; Fettinger, James_C; Berben, Louise_A (April 2022, ChemCatChem)

   Abstract Molecular design ultimately furnishes improvements in performance over time, and this has been the case for Rh‐ and Ir‐based molecular catalysts currently used in transfer hydrogenation (TH) reactions for fine chemical synthesis. In this report, we describe a molecular pincer ligand Al catalyst for TH, (I₂P²⁻)Al(THF)Cl (I₂P=diiminopyridine; THF=tetrahydrofuran). The mechanism for TH is initiated by two successive Al‐ligand cooperative bond activations of the O−H bonds in two molecules of isopropanol (ⁱPrOH) to afford six‐coordinate (H₂I₂P)Al(OⁱPr)₂Cl. Stoichiometric chemical reactions and kinetic experiments suggest an ordered transition state, supported by polar solvents, for concerted hydride transfer fromⁱPrO⁻to substrate. Metal‐ligand cooperative hydrogen bonding in a cyclic transition state is a likely support for the concerted hydride transfer event. The available data does not support involvement of an intermediate Al‐hydride in the TH. Proof‐of‐principle reactions including the conversion of isopropanol and benzophenone to acetone and diphenylmethanol with 90 % conversion in 1 h are described. The analogous hydride compound, (I₂P²⁻)Al(THF)H, also cleaves the O−H bond inⁱPrOH to afford (HI₂P⁻)Al(OⁱPr)H and (HI₂P⁻)Al(OⁱPr)₂, but no activity for catalytic TH was observed. 

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5. Ternary antimonide NaCd ₄ Sb ₃ : hydride synthesis, crystal structure and transport properties

   https://doi.org/10.1002/zaac.202200095  

   Courteau, Brittany; Gvozdetskyi, Volodymyr; Lee, Shannon; Cox, Tori; Zaikina, Julia V. (May 2022, Zeitschrift für anorganische und allgemeine Chemie)

   Abstract A new compound NaCd₄Sb₃(Rm,a=4.7013(1) Å,c=35.325(1), Å, Z=3,T=100 K) featuring the RbCd₄As₃structure type has been discovered in the Na−Cd−Sb system, in addition to the previously reported NaCdSb phase. NaCd₄Sb₃and NaCdSb were herein synthesized using sodium hydride as the source of sodium. The hydride method allows for targeted sample composition, improved precursor mixing, and an overall quicker synthesis time when compared to traditional methods using Na metal as a precursor. The NaCd₄Sb₃structure was determined from single‐crystal X‐ray diffraction and contained the splitting of a Cd site not seen in previous isostructural phases. NaCd₄Sb₃decomposes into NaCdSb plus melt at 766 K, as determined viain‐situhigh‐temperature PXRD. The electronic structure calculations predict the NaCd₄Sb₃phase to be semi‐metallic, which compliments the measured thermoelectric property data, indicative of ap‐type semi‐metallic material. The crystal structure, elemental analysis, thermal properties, and electronic structure are herein discussed in further detail. 

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