Ligand-Induced Fragmentation of Methylnickel Phenolates Containing a 2-Aldehyde Function: Structure of (3-tert-Butyl-5-methyl-2-oxobenzoyl)tris(trimethylphosphine)nickel

• Published in: Organometallics Vol. 13; no. 8; pp. 2944 - 2950
• Main Authors: Klein, Hans-Friedrich, Bickelhaupt, Alfred, Hammerschmitt, Birgit, Floerke, Ulrich, Haupt, Hans-Juergen
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.08.1994; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Organic chemistry; Organic compounds; Organometalloidal and organometallic compounds; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Transition metals derivatives; TRIMETHYLPHOSPHINE; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; COMPLEXES; Tertiary phosphine; Molecular structure; Nickel Organic compounds; Organic ligand; Metallocycle; Aryloxy complex; Transition metal Complexes; Acyl complex; Experimental study; X ray diffraction; Aldol; Mu complex; Alkoxy complex; Dinuclear complex; Reaction mechanism; Alkoxide; Benzenic compound; Crystalline structure
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om00020a009

O-bridging salicylaldehyde derivatives in dimeric methylnickel compounds NiMe(OR)(PMe3) showing equilibria of cis and trans forms (OR = 2-oxobenzaldehyde (1), 3-tert-butyl-5-methyl-2-oxobenzaldehyde (2), 3,5-di-tert-butyl-2-oxobenzaldehyde (3), 2-oxonaphthaldehyde (4)) spontaneously undergo, upon addition of trimethylphosphine, a fragmentation reaction forming 2-oxobenzoyl-C,O chelating ligands in 18-electron mononuclear complexes Ni(OC=O)(PMe3)3 (OC=O = 2-oxobenzoYl (5), 3-tert-butyl-5-methyl-2-oxobenzoyl (6), 3,5-di-tert-butyl-2-oxobenzoYl (7), 2-oxonaphthoyl (8)). The molecular structure of 6 contains pentacoordinate nickel with a chelate bite angle C-Ni-O = 85.5(1)-degrees. Dissociation of phosphine ligands in 5 gives Ni(OC=O)(PMe3)2 (9) and [Ni(OC)(PMe3)]2 (10), but no mobilization of carbonyl ligands could be observed in the presence of Ni(PMe3)4 as CO acceptor.