A Metal‐Containing N‐Heterocyclic Germylene Based on an Oxalamidine Framework. Issue 18 (2nd October 2018)

• Record Type: Journal Article
• Authors: Moos, Eric M. B.; Feuerstein, Wolfram; Krämer, Felix; Breher, Frank
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 644:Issue 18(2018)
• Page Start: 1115
• Page End: 1122
• Publication Date: 2018-10-02
• Subjects: Germylene -- Metalloligand -- Tetrylene -- Group 14 -- Rhodium; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201800298
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : A metal‐containing N‐heterocyclic germylene based on a N ‐mesityl (Mes)‐substituted oxalamidine framework is reported. The precursor (MesN=)2 C–C(–N(H)Mes)2 (1 H2 ) was converted into its rhodium complex [Rh(κ 2 N‐1 H2 )(cod)][OTf] (2 ) (cod = 1, 5‐cyclooctadiene; OTf = triflate) in 62 % isolated yield. Subsequent reaction of2 with Ge{N(SiMe3 )2 }2 gave the crystalline N‐heterocyclic germylene [Rh(cod)(μ‐1 )Ge][OTf] (3 ) in 50 % yield. The compounds under study were fully characterized by various methods, also including X‐ray crystallographic studies on single crystals of2 and3 . Density functional theory (DFT) calculations revealed that π conjugation in the bridging oxalamidine framework is increased and n(N)–p(Ge) π bonding is decreased upon κ 2 N metal coordination; a further weakening of the Ge–N bond occurs through triflate coordination to the Ge II atom. Nevertheless, preliminary coordination studies revealed that3 behaves as 2‐electron (L ‐type) germylene donor ligand. Treatment of3 with [Ir(cod)Cl]2 furnished the heterobimetallic complex [Rh(cod)(μ‐1 )Ge‐Ir(cod)Cl][OTf] (4 ), as evidenced by NMR spectroscopic investigations and DFT calculations. Abstract :