An Experimental and Theoretical Study of the Structures and Properties of [CDPMe‐Ni(CO)3] and [Ni2(CO)4(µ2‐CO)(µ2‐CDPMe)]. Issue 42 (6th November 2019)

• Record Type: Journal Article
• Authors: Flosdorf, Kimon; Jiang, Dandan; Zhao, Lili; Neumüller, Bernhard; Frenking, Gernot; Kuzu, Istemi
• Is Part Of: European journal of inorganic chemistry. Issue 42(2019)
• Page Start: 4546
• Page End: 4554
• Publication Date: 2019-11-06
• Subjects: Carbodiphosphoranes -- Carbonyl -- Nickel -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201900806
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The reaction of sym ‐dimethyltetraphenyl carbodiphosphorane (CDP Me ) with [Ni(CO)4 ] under standard conditions yields the CDP Me ‐ and carbon monoxide‐bridged dinickel pentacarbonyl complex [Ni2 (CO)4 (µ 2 ‐CO)(µ 2 ‐CDP Me )] (2 ). However, under an atmosphere of CO(g), reaction of [Ni(CO)4 ] with CDP Me gives the primal target complex [CDP Me ‐Ni(CO)3 ] (3 ). The complexes were examined in solution (ESI‐MS, NMR) and in the solid state (IR, X‐ray diffraction analysis). The resulting Tolman electronic parameter (TEP) and percentage buried volume value (% V bur ) of CDP Me are presented and compared with hexaphenyl carbodiphosphorane (CDP Ph ). DFT calculations were performed to analyze the bonding situation in complexes 2 and 3 . Abstract : Sym ‐dimethyltetraphenyl carbodiphosphorane (CDP Me ) reacts with [Ni(CO)4 ] yielding the dinickel pentacarbonyl complex [Ni2 (CO)4 (µ 2 ‐CO)(µ 2 ‐CDP Me )] (2 ) or the complex [CDP Me ‐Ni(CO)3 ] (3 ). The resulting Tolman electronic parameter (TEP) and percentage buried volume value (% V bur ) of CDP Me are presented. DFT calculations were performed to analyze the bonding situation in complexes 2 and 3 .