Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex
Dr. Yun Xiong
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorDr. Shenglai Yao
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorDr. Tibor Szilvási
Department of Chemical & Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706 USA
Search for more papers by this authorM. Sc. Ernesto Ballestero-Martínez
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorProf. Dr. Hansjörg Grützmacher
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1, Hönggerberg, 8093 Zürich, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Matthias Driess
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorDr. Yun Xiong
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorDr. Shenglai Yao
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorDr. Tibor Szilvási
Department of Chemical & Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706 USA
Search for more papers by this authorM. Sc. Ernesto Ballestero-Martínez
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorProf. Dr. Hansjörg Grützmacher
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1, Hönggerberg, 8093 Zürich, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Matthias Driess
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
Search for more papers by this authorAbstract
The first zwitterionic borata-bis(NHC)-stabilized phosphaketenyl germyliumylidene [(L2(O=C=P)Ge:] 2 (L2=(p-tolyl)2B[1-(1-adamantyl)-3-yl-2-ylidene]2) has been synthesized by salt-metathesis reaction of [L2(Cl)Ge:] 1 with sodium phosphaethynolate [(dioxane)nNaOCP]. Unexpectedly, its exposure to UV light affords, after reductive elimination of the entire PCO group, the unprecedented [L2Ge-GeL2] complex 3 in 54 % yields bearing the Ge22+ ion with Ge in the oxidation state +1. In addition, the 1,3-digermylium-2,4-diphosphacyclobutadiene [L2Ge(μ-P)2GeL2] 4 and bis(germyliumylidenyl)-substituted diphosphene [(L2Ge-P=P-GeL2)] 5 could also be obtained in moderate yields. The formation of 3–5 and their electronic structures have been elucidated with DFT calculations.
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