Probing substituent effects in phosphinoamine ligands using Mo(CO)5L complexes

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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)3CoY (R′ = iPr, 2,4,6-trimethylphenyl, 3,5-dimethylphenyl; R = Ph, iPr; 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(R2PNHR′) complexes has been synthesized (R = Ph, R′ = iPr (2a); R = iPr, R′ = iPr (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 ligands 1a-1g affords 2a-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.

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Lee, K. H., Napoline, J. W., Bezpalko, M. W., Foxman, B. M., & Thomas, C. M. (2015). Probing substituent effects in phosphinoamine ligands using Mo(CO)5L complexes. Polyhedron, 87, 354–360. https://doi.org/10.1016/j.poly.2014.12.005

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