Coordination Chemistry of [E(Idipp)]2+ Ligands (E = Ge, Sn): Metal Germylidyne [Cp*(CO)2W≡Ge(Idipp)]+ and Metallotetrylene [Cp*(CO)3W–E(Idipp)]+ Cations

Type
Article

Authors
Lebedev, Yury
Das, Ujjal
Schnakenburg, Gregor
Filippou, Alexander C.

KAUST Department
KAUST Catalysis Center (KCC)

Online Publication Date
2017-04-12

Print Publication Date
2017-04-24

Date
2017-04-12

Abstract
The synthesis and full characterization of the NHC-stabilized tungstenochlorostannylene [Cp*(CO)3W–SnCl(Idipp)] (1Sn), the NHC-stabilized chlorogermylidyne complex [Cp*(CO)2W═GeCl(Idipp)] (2), the tungsten germylidyne complex salt [Cp*(CO)2W≡Ge(Idipp)][B(C6H3-3,5-(CF3)2)4] (3), and the cationic metallostannylene [Cp*(CO)3W–Sn(Idipp)][Al(OC(CF3)3)4] (4Sn) are reported (Idipp = 2,3-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene, Cp* = η5-C5Me5). Metathetical exchange of SnCl2(Idipp) with Li[CpW(CO)3] afforded selectively 1Sn. Photolytic decarbonylation of the Ge analogue [Cp(CO)3W–GeCl(Idipp)] (1Ge) afforded the NHC-stabilized chlorogermylidyne complex (2), featuring a trigonal-planar coordinated germanium center and a W–Ge double bond (W–Ge 2.3496(5) Å). Chloride abstraction from 2 with Na[B(C6H3-3,5-(CF3)2)4] yielded the germylidyne complex salt 3, which contains an almost linear W–Ge–C1 linkage (angle at Ge = 168.7(1)°) and a W–Ge triple bond (2.2813(4) Å). Chloride elimination from 1Ge afforded the tungstenogermylene salt [Cp*(CO)3W–Ge(Idipp)][B(C6H3-3,5-(CF3)2)4] (4Ge), which in contrast to 1Ge could not be decarbonylated to form 3 despite the less strongly bound carbonyl ligands. The tin compounds 1Sn and 4Sn did not afford products bearing multiple W–Sn bonds. Treatment of 4Ge with Me2NC≡CNMe2 yielded unexpectedly the neutral germyl complex 5 containing a pendant 1-germabicyclo-[3,2,0]-hepta-2,5-diene ligand instead of the anticipated [2 + 1]-cycloaddition product at the Ge-center.

Citation
Lebedev YN, Das U, Schnakenburg G, Filippou AC (2017) Coordination Chemistry of [E(Idipp)]2+ Ligands (E = Ge, Sn): Metal Germylidyne [Cp*(CO)2W≡Ge(Idipp)]+ and Metallotetrylene [Cp*(CO)3W–E(Idipp)]+ Cations. Organometallics 36: 1530–1540. Available: http://dx.doi.org/10.1021/acs.organomet.7b00110.

Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (SFB813, “Chemistry at Spin Centers”) and University of Bonn for the financial support of this work. We appreciate the assistance of C. Schmidt, K. Prochnicki, and H. Spitz for recording the solution NMR spectra and A. Martens for the elemental microanalyses.

Publisher
American Chemical Society (ACS)

Journal
Organometallics

DOI
10.1021/acs.organomet.7b00110

Additional Links
http://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00110

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