Lutetium‐Methanediide‐Alkyl Complexes: Unique Reactivity toward Carbodiimide and Pyridine. Issue 17 (10th April 2019)

• Record Type: Journal Article
• Authors: Yan, Fangbin; Li, Shihui; Li, Lei; Zhang, Wanxi; Cui, Dongmei; Wang, Meiyan; Dou, Yanli
• Is Part Of: European journal of inorganic chemistry. Issue 17(2019)
• Page Start: 2277
• Page End: 2283
• Publication Date: 2019-04-10
• Subjects: rare‐earth metal -- alkylidene -- Carbenes -- carbodiimide -- pyridine; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201900197
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : We present the reactivity of four‐coordinate lutetium‐methanediide‐alkyl complexes 1 and 2 ((BODDI R )Lu2 (CH2 SiMe3 )2 (µ2 ‐CHSiMe3 )(THF)2, R = i Pr (1 ), R = Et (2 )). The reaction of 2 with N, N ‐diisopropylcarbodiimide ( i PrN=C=N i Pr) afforded a nucleophilic adduct 3 through insertion of three molecules of i PrN=C=N i Pr into the Lu‐µ2 ‐CHSiMe3 or Lu‐CH2 SiMe3 bonds. In subsequent three component reactions of 1 with N, N ‐dicyclohexylcarbodiimide (CyN=C=NCy) and pyridine, different addition patterns led to completely different products. Addition of CyN=C=NCy first and then pyridine into complex 1 resulted in the formation of (BODDI i Pr )Lu2 (CH2 SiMe3 )[CyNC(NCy)CHC(NCy)NCy(SiMe3 )][CyNC(C6 H4 N)NCy] (4 ) with insertion of two molecules of CyN=C=NCy into the Lu‐µ2 ‐CHSiMe3 bond. Reversing the addition sequence generated (BODDI i Pr )Lu2 [CyNC(NCy)C6 H4 N][CyNC(=CHSiMe3 )NCy)][CyNC(C6 H4 N)NCy] (5 ) with insertion of only one molecule of CyN=C=NCy into the Lu‐µ2 ‐CHSiMe3 bond. The possible mechanistic pathway to generate 4 was elucidated by DFT calculations. Abstract : The reactivity of a lutetium‐methanediide‐alkyl complex was exploited to efficiently construct two type of binuclear lutetium complexes. The outcome of these reactions strongly depends on the addition sequence of carbondiimide and pyridine and the reaction temperature.