title: Unexpected Photodegradation of a Phosphaketenyl-Substituted Germyliumylidene Borate Complex.
abstract: 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.
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Yun
authors.initials: Y
authors.lastname: Xiong
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Shenglai
authors.initials: S
authors.lastname: Yao
authors.affiliation: Department of Chemical & Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, WI, 53706, USA.
authors.forename: Tibor
authors.initials: T
authors.lastname: Szilvási
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Ernesto
authors.initials: E
authors.lastname: Ballestero-Martínez
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1, Hönggerberg, 8093, Zürich, Switzerland.
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher
authors.affiliation: Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
authors.forename: Matthias
authors.identifier: 0000-0002-9873-4103
authors.initials: M
authors.lastname: Driess
keywords: germanium; main-group chemistry; phosphagermyne; phosphinidene; phosphorus