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

Handle URI:
http://hdl.handle.net/10754/623814
Title:
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
Authors:
Lebedev, Yury ( 0000-0003-2985-6876 ) ; Das, Ujjal; Schnakenburg, Gregor; Filippou, Alexander C.
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[Cp*W(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.
KAUST Department:
KAUST Catalysis Center (KCC)
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.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
12-Apr-2017
DOI:
10.1021/acs.organomet.7b00110
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
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.
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00110
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorLebedev, Yuryen
dc.contributor.authorDas, Ujjalen
dc.contributor.authorSchnakenburg, Gregoren
dc.contributor.authorFilippou, Alexander C.en
dc.date.accessioned2017-05-31T11:23:07Z-
dc.date.available2017-05-31T11:23:07Z-
dc.date.issued2017-04-12en
dc.identifier.citationLebedev 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.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/acs.organomet.7b00110en
dc.identifier.urihttp://hdl.handle.net/10754/623814-
dc.description.abstractThe 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[Cp*W(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.en
dc.description.sponsorshipWe 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00110en
dc.titleCoordination Chemistry of [E(Idipp)]2+ Ligands (E = Ge, Sn): Metal Germylidyne [Cp*(CO)2W≡Ge(Idipp)]+ and Metallotetrylene [Cp*(CO)3W–E(Idipp)]+ Cationsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalOrganometallicsen
dc.contributor.institutionInstitut für Anorganische Chemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germanyen
kaust.authorLebedev, Yuryen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.