Dalton Transactions 2018-04-13

Three new types of transition metal carboranylamidinate complexes

Frank T Edelmann, Tim Rädisch, Nicole Harmgarth, Phil Liebing, María Joaquina Beltrán Leiva, Ramiro Arratia-Perez, Dayan Paez-Hernandez, Felix Engelhardt, Liane Hilfert, Florian Oehler, Sabine Busse

Index: 10.1039/C8DT01064A

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Abstract

Three new types of transition metal carboranylamidinate complexes are reported. The tetranuclear Mn(II) complexes Mn4Cl6[(o-C2B10H10)C(NiPr)(NHiPr)]2(THF)4•THF (2) was prepared by treatment of anhydrous MnCl2 with Li[(o-C2B10H10)C(NiPr)(NHiPr)] (= Li[HLiPr]) in THF, while the analogous reaction with FeCl2 afforded ionic [Li(DME)3][FeCl2{(o-C2B10H10)C(NiPr)(NHiPr)}] (3). The dinuclear Mo(II) complex Mo2[(o-C2B10H10)C(NiPr)-(NHiPr)]2(OAc)2•2THF (4), obtained from Mo2(OAc)4 and 2 equiv. of Li[HLiPr], represents the first example of a M–M multiple bond stabilized by carboranylamidinate ligands. All title compounds were structurally characterized by single-crystal X-ray diffraction. The M-M bonding in compound 4 has been further elucidated through Complete Active Space Self Consistent Field (CASSCF) calculations.