Monomeric Phosphido and Phosphinidene Complexes of Nickel

• Published in: Journal of the American Chemical Society Vol. 124; no. 15; pp. 3846 - 3847
• Main Authors: Melenkivitz, Rory, Mindiola, Daniel J, Hillhouse, Gregory L
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 17.04.2002
• Subjects: Chemistry; Condensed matter: structure, mechanical and thermal properties; Coordination compounds; Exact sciences and technology; Inorganic chemistry and origins of life; Inorganic compounds; Metal complexes; Physics; Preparations and properties; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Phosphido complex; Nickel Complexes; Molecular structure; Ditertiary phosphine; Organic ligand; Transition metal Complexes; X ray diffraction; Crystalline structure
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja017787t

An unusual family of three-coordinate, d8 and d9 nickel phosphido and phosphinidene complexes containing the chelating 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand and a terminal PR2 - or PR2- ligand have been prepared. The complexes (dtbpe)Ni{P(t-Bu)2} (2), [(dtbpe)Ni{P(t-Bu)2}+][PF6 -] (3), [(dtbpe)Ni{P(H)(dmp)}+][PF6 -] (5), and (dtbpe)Ni{P(dmp)} (6) have been structurally characterized by single-crystal X-ray diffraction methods. The three-coordinate d8 complexes exhibit Ni−P bond lengths and ligand geometries that indicate they participate in symmetry-allowed ligand-to-metal π bonding involving phosphorus p-electrons and a metal-orbital of π symmetry that lies in the Ni coordination plane. Compound 6 is a rare example of a late-transition-metal terminal phosphinidene complex.