Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide We have studied the cross-coupling reaction of C( sp n )–X bonds (n = 1–3; X = F, Cl, Br, I) mediated by the model iron-d 8 catalyst Fe(CO) 4 with the archetypal model substrates H 3 C–CH 2 –X, H 2 C═CH–X, and HC≡C–X, utilizing relativistic density functional theory at ZORA-OPBE/TZ2P. The barrier of the oxidative-addition step decreases as the C( sp n )–X bond varies from X = F to Cl to Br to I and from C( sp 3 ) to C( sp 2 ) to C( sp ). Activation strain and energy decomposition analyses uncover that the lowering of the reaction barrier from X = F to I is caused by (i) a weaker C( sp n )–X bond that needs to be broken, (ii) enhanced HOMO–LUMO interactions, and (iii) a stronger electrostatic attraction between the catalyst and the substrate due to the more diffuse electron density and higher nuclear charge of the X atom when varying from X = F to I.
Source: Organometallics
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funder: Exacte en Natuurwetenschappen
OpenAlex ID: W4403764702