Bis(alkyl) scandium and yttrium complexes coordinated by an amidopyridinate ligand: synthesis, characterization and catalytic performance in isoprene polymerization, hydroelementation and carbon dioxide hydrosilylation

Abstract

Highly versatile and robust organolanthanides as catalysts or catalyst precursors for a variety of challenging transformations.

Mild and Selective Carbon Dioxide Hydroboration to Methoxyboranes Catalyzed by Mn(I) PNP Pincer Complexes

“…This is then sequentially converted to the final methoxyborane product by metal‐free steps in the presence of HBpin and a Lewis acid, that may in turn assist the activation of the B−H bond. A similar mechanism has been recently proposed for CO 2 hydrosilylation in the presence of B(C 6 F 5 ) 3 . DFT calculations to describe the full catalytic cycle and pinpoint the role of the N−H moiety will be carried out and reported in due time.…”

“…A similar mechanism has been recently proposed for CO 2 hydrosilylation in the presence of B(C 6 F 5 ) 3 . [50] DFT calculations to describe the full catalytic cycle and pinpoint the role of the NÀ H moiety will be carried out and reported in due time.…”

Reported Catalytic Hydrofunctionalizations that Proceed in the Absence of Catalysts: The Importance of Control Experiments

“… [38] Besides, the reaction was also reported using known catalyst based systems which include anhydrous cerium(III) chloride (entry 2), [39] scandium(III) triflate (entry 3), [40] PPh 3 AuNTf 2 , [41] ionic liquids (entry 4 and 5), [36] Ru‐based visible light photocatalyst (entry 6), [42] etc. The same reaction using Sc‐based catalyst took 48 h at 70 °C (entry 7), [43] which proceeded to completion within 30 min at 35 °C in the absence of a catalyst [38] …”

Partnering a Three‐Coordinate Gallium Cation with a Hydroborate Counter‐Ion for the Catalytic Hydrosilylation of CO2

“…Thus, a variety of homogenous catalytic systems based on metals (Pd/Pt, [14–17] Rh, [18] Re, [19, 20] Ru, [21–26] Ir, [8, 27–30] Co, [13, 31] Mn, [12] Zr, [32, 33] Cu, [34–38] Ni, [39–42] Sc, [43–46] Zn, [47–57] Mg [57, 58] and Sr [59] ), Lewis acids, [60–66] frustrated Lewis pairs (FLPs), [67, 68] organo‐catalysts, [69–75] alkali metal carbonates, [76, 77] and metal borohydrides [78] have been investigated for this process. Many of these catalytic systems feature reactive metal hydride or alkyl groups, which effect the initial activation of CO 2 via insertion.…”

“…[7][8][9] In addition, the use of silanesh as allowed for the development of catalytic systemsw hich exercise greaterc ontrolo ver selectivity for products with different carbon oxidationl evels,i ncluding silyl formates,s ilyl acetals, methoxysilanes and methane (which is formed in conjunction with bis(silyl)ethers). [8][9][10][11][12][13] Thus, av arietyo fh omogenousc atalytic systemsb ased on metals (Pd/Pt, [14][15][16][17] Rh, [18] Re, [19,20] Ru, [21][22][23][24][25][26] Ir, [8,[27][28][29][30] Co, [13,31] Mn, [12] Zr, [32,33] Cu, [34][35][36][37][38] Ni, [39][40][41][42] Sc, [43][44][45][46] Zn, [47][48][49]…”