Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties
| dc.authorid | 0000-0002-2841-0197 | |
| dc.authorid | 0000-0002-0424-4673 | |
| dc.authorid | 0000-0001-5582-3475 | |
| dc.contributor.author | Yıldız, Cem Burak | |
| dc.contributor.author | Khan, Souvik | |
| dc.contributor.author | Gonnade, Rajesh G. | |
| dc.contributor.author | Majumdar, Moumita | |
| dc.date.accessioned | 2024-04-25T06:23:50Z | |
| dc.date.available | 2024-04-25T06:23:50Z | |
| dc.date.issued | 2023 | |
| dc.department | Teknik Bilimler Meslek Yüksekokulu | |
| dc.description.abstract | We report the first examples of intramolecular phosphine-stabilized tetra-coordinated germanium(iv) di-cationic compounds: [LiPr2Ge][CF3SO3]23iPr and [LPh2Ge][CF3SO3]23Ph (LiPr = 6-(diisopropylphosphanyl)-1,2-dihydroacenaphthylene-5-ide; LPh = 6-(diphenylphosphanyl)-1,2-dihydroacenaphthylene-5-ide). The step wise synthetic strategy involves the isolation of neutral and mono-cationic Ge(iv) precursors: [LiPr2GeCl][X] (X = GeCl31iPr, OTf 2iPr), [LPh2GeCl2] 1Ph and [LPh2GeCl][OTf] 2Ph. Both 3iPr and 3Ph exhibit constrained spiro-geometry. DFT studies reveal the dispersion of di-cationic charges over P-Ge-P sites. Anion or Lewis base binding occurs at the Ge site resulting in relaxed distorted trigonal bipyramidal/tetrahedral geometry. 3iPr and 3Ph activate the Si-H bond initially at the P-site. The hydride ultimately migrates to the Ge-site rapidly giving [LPh2GeH][CF3SO3] 3PhH, while sluggishly forming [LiPr2GeH][CF3SO3] 3iPrH. Compounds 3iPr and 3Ph were tested as catalysts for the hydrosilylation of aromatic aldehydes. While catalytic hydrosilylation proceeded via the initial Et3Si-H bond activation in the case of 3iPr, compound 3Ph as a catalyst showed a masked Frustrated Lewis Pair (FLP) type reactivity in the catalytic cycle. | |
| dc.identifier.doi | 10.1039/d3sc03717g | |
| dc.identifier.endpage | 13764 | en_US |
| dc.identifier.issn | 2041-6520 | |
| dc.identifier.issue | 47 | en_US |
| dc.identifier.pmid | 38075658 | |
| dc.identifier.scopusquality | Q1 | |
| dc.identifier.startpage | 13755 | en_US |
| dc.identifier.uri | https:/dx.doi.org10.1039/d3sc03717g | |
| dc.identifier.uri | https://hdl.handle.net/20.500.12451/11705 | |
| dc.identifier.volume | 14 | en_US |
| dc.identifier.wos | WOS:001109527100001 | |
| dc.identifier.wosquality | Q1 | |
| dc.indekslendigikaynak | Web of Science | |
| dc.indekslendigikaynak | Scopus | |
| dc.indekslendigikaynak | PubMed | |
| dc.language.iso | en | |
| dc.publisher | Royal Society of Chemistry | |
| dc.relation.ispartof | Chemical Science | |
| dc.relation.publicationcategory | Makale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı | |
| dc.rights | info:eu-repo/semantics/openAccess | |
| dc.subject | Intramolecular donor-stabilized | |
| dc.title | Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties | |
| dc.type | Article |
