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Insertion Reactions of NH3 and H2O with the Ferriogermylenes ArGeFeCp(CO)2 (Ar=ArMe6 (-C6H3-(C6H2-2,4,6-Me3)2) or AriPr4(-C6H3-(C6H3-2,6-iPr2)2); Cp = η5-C5H5): Structural Isomerism and Polymorphism in a Metallogermylene

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ORGANOMETALLICS
卷 40, 期 20, 页码 3472-3479

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AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.1c00475

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  1. Office of Basic Energy Sciences, U.S. Department of Energy [DE-FG02-07ER4675, 0840444]

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The ferriogermylenes react with NH3 and water to form insertion products with unique structural features, which were characterized using NMR, UV-vis, IR spectroscopy, and X-ray crystallography.
The ferriogermylenes ArGeFeCp(CO)(2) (Ar = -C6H3-(C6H2-2,4,6-Me-3)(2) (Ar-Me6 (1a)), Ar = -C6H3-(C6H3-2,6-Pr-i(2))(2) (Ar-iPr4 (1b))) (Cp =eta(5)-C5H5) react with an excess of NH3(l) to form the insertion products ArGe(NH2)(H)FeCp(CO)(2) (Ar = Ar-Me6 (2a) or Ar-iPr4 (2b)). Similarly, ferriogermylene 1a reacts with water to form the insertion product (ArGe)-Ge-Me6(OH)(H)FeCp(CO)(2) (3). Unusually, crystals of 1a exist as three different polymorphs whose structures differ primarily in their C-ipso-Ge-Fe bond angles. Complexes 1-3 were characterized by NMR, UV-vis, IR spectroscopy, and X-ray crystallography.

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