Synthesis and Structures of Scandium and Lutetium Benzyl Complexes

Abstract

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Potential Precursors for Terminal Methylidene Rare‐Earth‐Metal Complexes Supported by a Superbulky Tris(pyrazolyl)borato Ligand

“…Other rare solid‐state structures of monomeric but heteroleptic Tp‐based rare‐earth‐metal complexes as [Tp R,R Ln(Danip)(CH 2 SiMe 3 )] (R=Me or R=H, Ln=Yb, Danip=2,6‐di( o ‐anisol)phenyl)) display similar bond lengths (Yb−C ipso : 2.414(3)–2.438(4)/2.402(4)–2.435(5) Å; Yb−C(neosilyl): 2.379(4)–2.392(4)/2.359(4)–2.368(4) Å) taking into account the metal‐ion size . The Lu−C(benzyl) bond length (2.412(3) Å) in 9‐Lu matches that in Lu(CH 2 Ph) 3 (THF) 3 (2.404(7)–2.413(5) Å) and Lu(CH 2 Ph) 3 (THF) 2 (2.380(3)–2.404(3) Å) but is slightly elongated compared with Cp*Lu(CH 2 Ph) 2 (THF) (2.378(2)–2.386(2) Å; Cp*=C 5 Me 5 ) . Furthermore, there is no significant secondary interaction between Lu1 and the ipso carbon atom C27 for 9‐Lu , as suggested by the Lu1⋅⋅⋅C27 distance of 3.314 Å and the Lu‐C(CH 2 )‐C27 angle (114.3(2)°).…”

Formation and Reactivity of a C‐P‐N‐Sc Four‐Membered Ring: H2, O2, CO, Phenylsilane, and Pinacolborane Activation

“…The C‐P‐N‐Sc four‐membered ring is nearly coplanar with the N3‐Sc‐C1 and N3‐P‐C1 angles of 77.93(10)° and 98.75(12)°, respectively. The Sc−C1 distance (2.284(3) Å) is longer than the Sc−C bonds in complex 2 (2.205(3) Å on average), but close to those in Sc(CH 2 Ph) 3 (THF) 3 (2.311(3) Å on average) . The Sc−N3 distance (2.014(2) Å) is close to those in the scandium anilido complexes, such as [{ t BuCN(DIPP)} 2 CHSc(NH(DIPP))(CH 3 )] and [CH 3 C{N(DIPP)}CHC(CH 3 )(NCH 2 CH 2 NMe 2 )(CH 3 )Sc(NH(DIPP))(CH 3 )] (2.047(3) Å) .…”

Reactivity and Properties of Metal Complexes Enabled by Flexible and Redox-Active Ligands with a Ferrocene Backbone

“…43,59,78 (NN fc ): Initially, we sought out to employ salt metathesis between K 2 (NN fc ) and MX 3 (THF) y (M = rare-earth metal, X = Cl or Br, y = 3-4) and found that the reaction was poorly reproducible and usually accompanied by a side product, the bis-ligand-adduct K[(NN fc ) 2 M], which was difficult to remove. 81 At the same time, we and other groups independently published protocols to prepare key metal benzyl synthetic intermediates, M(CH 2 Ar) 3 (M = Sc, Y, La, and Lu, Ar = Ph, 3,5-C 6 H 3 Me 2 ), from MX 3 (X = Cl, Br), [95][96][97][98] which, in turn were obtained directly from metal oxides. 99 The acidbase reaction between M(CH 2 Ar) 3 41,46 This in situ method was much more efficient: the preparation time was reduced to 1 day from 1 week and the overall yield was improved for all rare-earth metals, Scheme 2a.…”