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• W2056598483 abstract "The 95Mo NMR spectra of cationic molybdenum phosphenium complexes have been measured. Going from fac-[(bpy)(CO)3Mo{PN(Me)CH2CH2NMe(OMe)}] (1a) to fac-[(bpy)(CO)3Mo{PN(Me)CH2CH2NMe}]+ (fac-1b) to mer-[(bpy)(CO)3Mo{PN(Me)CH2CH2NMe}]+ (mer-1b) causes deshielding of the 95Mo doublet resonance (δ −1081 (1a), −1049 (fac-1b), −1015 (mer-1b)), an increase in the Mo−P coupling constant (193 Hz (1a), 264 Hz (fac-1b), 337 Hz (mer-1b)), and an increase in the line width (35 Hz (1a), 90 Hz (fac-1b), 300 Hz (mer-1b)). The conversion of fac-[(bpy)(CO)3Mo{PN(Me)CH2CH2O(OMe)}] (fac-2a) into mer-[(bpy)(CO)3Mo{PN(Me)CH2CH2O}]+ (mer-2b) showed a similar trend in 95Mo NMR data, though fac-[(bpy)(CO)3Mo{PN(Me)CH2CH2O}]+ was not detected in this case. mer-2b exhibits the largest Mo−P coupling constant (343 Hz) among those reported so far. These changes can be reasonably attributed to a dominant contribution from the imbalance of electron density at the Mo in the Ramsey equation due to a significant double-bond character between the molybdenum and the phosphenium phosphorus. Comparison of coupling constants between M and a phosphenium P in [(bpy)(CO)3M{PN(Me)CH2CH2NMe}]+ (M = Mo, W) revealed that the ratio 1JW-P/1JMo-P is 1.67, which is very close to the ratio (1.76) reported for many series of M−phosphine (or phosphite) complexes (M = Mo, W). The 95Mo NMR spectra of cis- and trans-[(bpy)(CO)2Mo{PN(Me)CH2CH2X(OMe)}{PN(Me)CH2CH2X}]+ (X = NMe, cis-1c, trans-1c; X = O, cis-2c, trans-2c) have also been measured; the chemical shifts are understood similarly in terms of the imbalance of electron density at Mo." @default.
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• W2056598483 date "1996-05-14" @default.
• W2056598483 modified "2023-09-25" @default.
• W2056598483 title "⁹⁵Mo NMR Studies on Cationic Phosphenium Complexes of Molybdenum" @default.
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• W2056598483 doi "https://doi.org/10.1021/om950807d" @default.
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