Lutetium‐Methanediide‐Alkyl Complexes: Synthesis and Chemistry. Issue 47 (5th October 2014)

• Record Type: Journal Article
• Authors: Li, Shihui; Wang, Meiyan; Liu, Bo; Li, Lei; Cheng, Jianhua; Wu, Chunji; Liu, Dongtao; Liu, Jingyao; Cui, Dongmei
• Is Part Of: Chemistry. Volume 20:Issue 47(2014)
• Page Start: 15493
• Page End: 15498
• Publication Date: 2014-10-05
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404809
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The first four‐coordinate methanediide/alkyl lutetium complex (BODDI)Lu<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>(μ<sub>2</sub>‐CHSiMe<sub>3</sub>)(THF)<sub>2</sub> (BODDI=ArNC(Me)CHCOCHC(Me)NAr, Ar=2, 6‐<italic>i</italic>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (<bold>1</bold>) was synthesized by a thermolysis methodology through α‐H abstraction from a Lu–CH<sub>2</sub>SiMe<sub>3</sub> group. Complex <bold>1</bold> reacted with equimolar 2, 6‐<italic>i</italic>PrC<sub>6</sub>H<sub>3</sub>NH<sub>2</sub> and Ph<sub>2</sub>CO to give the corresponding lutetium bridging imido and oxo complexes (BODDI)Lu<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>(μ<sub>2</sub>‐<italic>N</italic>‐2, 6‐<italic>i</italic>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)(THF)<sub>2</sub> (<bold>2</bold>) and (BODDI)Lu<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>(μ<sub>2</sub>‐O)(THF)<sub>2</sub> (<bold>3</bold>). Treatment of <bold>3</bold> with Ph<sub>2</sub>CO (4 equiv) caused a rare insertion of Lu–μ<sub>2</sub>‐O bond into the CO group to afford a diphenylmethyl diolate complex <bold>4</bold>. Reaction of <bold>1</bold> with PhN=CO (2 equiv) led to the migration of SiMe<sub>3</sub> to the amido nitrogen atom to give complex (BODDI)Lu<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>)<sub>2</sub>‐μ‐{PhNC(O)CHC(O)NPh(SiMe<sub>3</sub>)‐κ<sup>3</sup>N, O, O}(THF) (<bold>5</bold>). Reaction of <bold>1</bold> with <italic>t</italic>BuNC formed an unprecedented product (BODDI)Lu<sub>2</sub>(CH<sub>2</sub>SiMe<sub>3</sub>){μ<sub>2</sub>‐[η<sup>2</sup>:η<sup>2</sup>‐<italic>t</italic>BuNC(=CH<sub>2</sub>)SiMe<sub>2</sub>CHCN<italic>t</italic>Bu‐κ<sup>1</sup>N]}(<italic>t</italic>BuNC)<sub>2</sub> (<bold>6</bold>) through a cascade reaction of NC bond insertion, sequential cyclometalative γ‐(sp<sup>3</sup>)‐H activation, CC bond formation, and rearrangement of the newly formed carbene intermediate. The possible mechanistic pathways between <bold>1</bold>, PhNCO, and <italic>t</italic>BuNC were elucidated by DFT calculations.</p> </abstract>