Iridium Halide Complexes [1, 1‐X2‐8‐SMe2‐1, 2, 8‐IrC2B9H10]2 (X = Cl, Br, I): Synthesis, Reactivity and Catalytic Activity. Issue 38 (1st August 2017)

• Record Type: Journal Article
• Authors: Molotkov, Alexander P.; Vinogradov, Mikhail M.; Moskovets, Alexey P.; Chusova, Olga; Timofeev, Sergey V.; Fastovskiy, Vasilii A.; Nelyubina, Yulia V.; Pavlov, Alexander A.; Chusov, Denis A.; Loginov, Dmitry A.
• Other Names: Bregadze Vladimir I. guestEditor.; Xie Zuowei guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 38/39(2017)
• Page Start: 4635
• Page End: 4644
• Publication Date: 2017-08-01
• Subjects: C–H activation -- Iridium -- Metallacarboranes -- Metal complex catalysis -- Halides; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700498
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The reactions of thallium salt Tl[7‐SMe2 ‐7, 8‐C2 B9 H10 ] with [(cod)RhCl]2 and [Cp*RuCl]4 are accompanied by room‐temperature polyhedral rearrangement, giving rhoda‐ and ruthenacarboranes 1‐cod‐8‐SMe2 ‐1, 2, 8‐RhC2 B9 H10 (2 ) and 1‐Cp*‐8‐SMe2 ‐1, 2, 8‐RuC2 B9 H10 (3 ), respectively. According to DFT calculations, the rearrangement could be attributed to the triangular face rotation mechanism. The reaction of iridium derivative 1‐cod‐8‐SMe2 ‐1, 2, 8‐IrC2 B9 H10 (1 ) with anhydrous hydrohalic acids HX (X = Cl, Br, I) results in the dimeric halide iridacarboranes [1, 1‐X2 ‐8‐SMe2 ‐1, 2, 8‐IrC2 B9 H10 ]2 [4a –c ; X = Cl (a ), Br (b ), I (c )]. Bromide4b reacts with Tl[Tl(η‐7, 8‐C2 B9 H11 )] and TlCp giving iridacarboranes 8′‐SMe2 ‐1, 1′‐Ir(2, 3‐C2 B9 H11 )(2′, 8′‐C2 B9 H10 ) (5 ) and 1‐Cp‐8‐SMe‐1, 2, 8‐IrC2 B9 H10 (6 ). The formation of the latter compound is accompanied by demethylation of the SMe2 substituent. The structures of2, 3, 5 and6 were determined by single‐crystal X‐ray diffraction. Iridacarboranes4b and [1, 1‐Br2 ‐4‐SMe2 ‐1, 2, 3‐IrC2 B9 H10 ]2 (7 ) catalyze the dimerization of diphenylacetylene, giving 1, 2, 3‐triphenylnaphthalene in 20–24 % yields. Compounds4b and7 also effectively catalyze the reductive amination reaction between aldehydes (or ketones) and primary (or secondary) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in high yields (60–85 %). Abstract : Iridium halide complexes [1, 1‐X2 ‐8‐SMe2 ‐1, 2, 8‐IrC2 B9 H10 ]2 (X = Cl, Br, I) were synthesized by reaction of the cyclooctadiene derivative 1‐cod‐8‐SMe2 ‐1, 2, 8‐IrC2 B9 H10 with anhydrous hydrohalic acids HX. These complexes have proven to be effective catalysts for the dimerization of alkynes and the reductive amination of aldehydes and ketones.