Probing substituent effects in phosphinoamine ligands using Mo(CO)5L complexes. (17th February 2015)

• Record Type: Journal Article
• Authors: Lee, Kyle H.; Napoline, J.W.; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M.
• Is Part Of: Polyhedron. Volume 87(2015)
• Page Start: 354
• Page End: 360
• Publication Date: 2015-02-17
• Subjects: Metal carbonyl -- Phosphinoamine -- Molybdenum -- Infrared spectroscopy -- Ligand properties; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2014.12.005
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A series of Mo(CO)5 L complexes have been synthesized, where L = a series of phosphinoamine ligands, R2 PNHR′. The effects of variations in phosphorus and nitrogen substituents on phosphine donor properties have been established using infrared CO stretches as a spectroscopic probe. Abstract: Recent work has revealed substantial differences in the structure, spectroscopic properties, and reactivity of heterobimetallic Zr/Co complexes of the general form XZr(R′NPR2 )3 CoY (R′ = i Pr, 2, 4, 6-trimethylphenyl, 3, 5-dimethylphenyl; R = Ph, i Pr; X, Y = halides or neutral donor ligands) as a function of nitrogen and phosphorus donor atom substituents. To probe the electronic differences between these ligands, a series of Mo(CO)5 (R2 PNHR′) complexes has been synthesized (R = Ph, R′ = i Pr (2a ); R = i Pr, R′ = i Pr (2b ), 2, 4, 6-trimethylphenyl (2c ), 3, 5-dimethylphenyl (2d ), 4-methylphenyl (2e ), 4-trifluoromethylphenyl (2f ), 4-methoxyphenyl (2g )). Thermolysis of Mo(CO)6 with the corresponding phosphinoamine ligands1a –1g affords2a –2g . The infrared carbonyl stretching frequencies of these complexes have been compared to probe the effects of phosphorus and nitrogen substituents on the electronic properties of the phosphinoamine ligands.