Reduction of [Cp*Sb]4 with Subvalent Main‐Group Metal Reductants: Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge‐Missing Sb4 Units. Issue 10 (26th January 2017)

• Record Type: Journal Article
• Authors: Ganesamoorthy, Chelladurai; Krüger, Julia; Wölper, Christoph; Nizovtsev, Anton S.; Schulz, Stephan
• Is Part Of: Chemistry. Volume 23:Issue 10(2017)
• Page Start: 2461
• Page End: 2468
• Publication Date: 2017-01-26
• Subjects: antimony -- cluster compounds -- main-group elements -- subvalent compounds -- Zintl ions; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605547
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: [Cp*Sb]4 (Cp*=C5 Me5 ) reacts with [L 1 Mg]2 and L 2 Ga with formation of [(L 1 Mg)4 ( μ4, η 1:2:2:2 ‐Sb4 )] (L 1 = i Pr2 NC[N(2, 6‐ i Pr2 C6 H3 )]2, 1 ) and [(L 2 Ga)2 ( μ, η 2:2 ‐Sb4 )] (L 2 =HC[C(Me)N(2, 6‐ i Pr2 C6 H3 )]2, 2 ). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of1 occurred by elimination of the Cp* anion and formation of Cp*MgL 1, while2 was formed by reductive elimination of Cp*2 and oxidative addition of L 2 Ga to the Sb4 unit.1 and2 were characterized by heteronuclear NMR spectroscopy and single‐crystal X‐ray diffraction, and their bonding situation was studied by quantum chemical calculations. Abstract : Go four antimony : [(L 1 Mg)4 ( μ4, η 1:2:2:2 ‐Sb4 )] (L 1 =( N ‐ i Pr2 )C[N(2, 6‐ i Pr2 C6 H3 )]2, 1 ) and [(L 2 Ga)2 ( μ, η 2:2 ‐Sb4 )] (L 2 =HC[C(Me)N(2, 6‐ i Pr2 C6 H3 )]2, 2 ) containing adjacent and opposite edge‐missing Sb4 tetrahedrons were obtained from reactions of [Cp*Sb]4 with [L 1 Mg]2 and L 2 Ga. They were characterized by single‐crystal X‐ray diffraction and their bonding situation was investigated by quantum chemical calculations.