Size Matters: Synthesis of Group 13 Metal‐Substituted Dipnictanes by E‐C Bond Homolysis
Christoph Helling, Christoph Wölper, Stephan Schulz
Abstract
Pnictanes Cp*(Ph)ECl (E = As 1 , Sb 2 ; Cp* = C 5 Me 5 ) react with group 13 diyls LM (M = Al, Ga, In; L = HC[C(Me)N(Dip)] 2 , Dip = 2,6‐ i Pr 2 C 6 H 3 ) 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 ).
Topics & Concepts
HomolysisChemistryBond cleavageCrystallographyMetalSingle crystalCrystal structureBond lengthStereochemistryMedicinal chemistryRadicalCatalysisOrganic chemistrySynthesis and characterization of novel inorganic/organometallic compoundsOrganometallic Complex Synthesis and CatalysisCoordination Chemistry and Organometallics