| | 1 | Author
| Thomas Mack, Karl Peters, Hans-Georg Von Schnering | Requires cookie* | | | Title
| Zur Stereochemie von Diazadien-Metall-Komplexen, V [1] Molekülstrukturen und CO-Kraftkonstanten nicht-starrer Chrom-, Molybdän- und Wolframcarbonylderivate DAD M(CO)3(*CO) (*C0 = 12 C0, 13 C0, C 18 0) Stereochemistry of Diazadiene Metal Complexes, V [lj Molecular Structures and CO Force Constants of Non-Rigid Chromium, Molybdenum and Tungsten Carbonyl Derivatives DAD M(CO)3(*CO) (*C0 = 12 CO, 13 C0, C 18 0) Heindirk torn Dieck  | | | | Abstract
| Diazadiene metal tetracarbonyls, DAD M(CO)4, (M = Cr, Mo, W; DAD = R-N = CH-CH = NR with aliphatic and aromatic substituents R) show equi-distribution of one labelled CO when synthesized from fac-DAD M(CO)3(CH3CN) as a consequence of intramolecular CO site exchange. The structures of two Mo-complexes (1: R = iso-propyl; 2: R = 2,6-diisopropylphenyl) with DAD's of different bulkiness have been solved by X-ray methods. From the infrared solution spectra, including those of isotopically labelled (13 CO, C 18 0) compounds, all of the force constants ki, k2, ktt, kcc and kct bave been calculated independently. The ratios of interaction force constants deviate sharply from Cotton-Kraihanzel assumptions, perhaps because of the substantial deviation of the iraws-pair of CO groups from linearity (1: 154.5°, 2: 147.9°). The solid state N-Mo, Mo-C and C-0 bond lengths are neither in agreement with the generally accepted picture for donor/acceptor influences nor with typical IR data and force constant interpretations. (2 with higher v(CO) and ki, k2 has the longer CO bonds and shorter Mo-C bonds than 1.) The force constant sets have been used to calculate CO frequencies for over 60 labelled compounds with good accuracy (Av < 2 cm -1). | | | |
Reference
| Z. Naturforsch. 38b, 568—579 (1983); eingegangen am 3. Dezember 1982 | | | |
Published
| 1983 | | | |
Keywords
| Diazadiene Chromium, Molybdenum and Tungsten Carbonyls, X-Ray, Isotopically Labelled Carbonyls | | | |
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| ZNB-1983-38b-0568 | | | | Volume
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