Size Matters: Synthesis of Group 13 Metal‐Substituted Dipnictanes by E‐C Bond Homolysis. Issue 44 (16th September 2020)

• Record Type: Journal Article
• Authors: Helling, Christoph; Wölper, Christoph; Schulz, Stephan
• Is Part Of: European journal of inorganic chemistry. Issue 44(2020)
• Page Start: 4225
• Page End: 4235
• Publication Date: 2020-09-16
• Subjects: Main group elements -- Antimony -- Arsenic -- Heterometallic complexes -- Radicals; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202000747
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Pnictanes Cp*(Ph)ECl (E = As 1, Sb 2 ; Cp* = C5 Me5 ) react with group 13 diyls LM (M = Al, Ga, In; L = HC[C(Me)N(Dip)]2, Dip = 2, 6‐ i Pr2 C6 H3 ) with oxidative addition of the E‐Cl bond to a unique series of metalylpnictanes [L(Cl)M](Ph)ECp* (E = As, M = Al 3, Ga 4, In 5 ; E = Sb, M = Al 6, Ga 7, In 8 ). Thermal treatment of 4 and 6 –8 results in homolytic E‐C bond scission with Cp* radical liberation, yielding the corresponding dipnictanes {[L(Cl)M](Ph)E}2 (E = As, M = Ga 9 ; E = Sb, M = Al 10, Ga 11, In 12 ). Compounds 1 –12 were characterized by NMR ( 1 H, 13 C) and IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction (3 –12 ). Abstract : A series of metalylpnictanes [L(Cl)M](Ph)ECp* (M = Al, Ga, In; E = As Sb), which are generally accessible by oxidative addition reaction of Cp*(Ph)ECl and group 13 diyls LM, is converted into the corresponding dipnictanes {[L(Cl)M](Ph)E}2 by thermal treatment. The study reveals the distinct influence of ligand size on the reaction mechanism and product formation.