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Cooperative N-H bond activation by amido-Ge(ii) cations.
Dalton Trans. 2020 Jul 17; 49(27):9495-9504.DT

Abstract

N-heterocyclic carbene (NHC) and tertiary phosphine-stabilized germylium-ylidene cations, [R(L)Ge:]+, featuring tethered amido substituents at R have been synthesized via halide abstraction. Characterization in the solid state by X-ray crystallography shows these systems to be monomeric, featuring a two-coordinate C,N- or P,N-ligated germanium atom. The presence of the strongly Lewis acidic cationic germanium centre and proximal amide function allows for facile cleavage of N-H bonds in 1,2-fashion: the products resulting from reactions with carbazole feature a tethered secondary amine donor bound to a three-coordinate carbazolyl-GeII centre. In each case, addition of the components of the N-H bond occurs to the same face of the germanium amide function, consistent with a coordination/proton migration mechanism. Such as sequence is compatible with the idea that substrate coordination via the pπ orbital at germanium reduces the extent of N-to-Ge π donation from the amide, thereby enhancing the basicity of the proximal N-group.

Authors+Show Affiliations

Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk and Department of Chemistry, Nanoscience Center, University of Jyväskylä, P. O. Box 35, FI-40014 University of Jyväskylä, Finland.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK. simon.aldridge@chem.ox.ac.uk.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32608471

Citation

Zhou, Xueer, et al. "Cooperative N-H Bond Activation By amido-Ge(ii) Cations." Dalton Transactions (Cambridge, England : 2003), vol. 49, no. 27, 2020, pp. 9495-9504.
Zhou X, Vasko P, Hicks J, et al. Cooperative N-H bond activation by amido-Ge(ii) cations. Dalton Trans. 2020;49(27):9495-9504.
Zhou, X., Vasko, P., Hicks, J., Fuentes, M. Á., Heilmann, A., Kolychev, E. L., & Aldridge, S. (2020). Cooperative N-H bond activation by amido-Ge(ii) cations. Dalton Transactions (Cambridge, England : 2003), 49(27), 9495-9504. https://doi.org/10.1039/d0dt01960g
Zhou X, et al. Cooperative N-H Bond Activation By amido-Ge(ii) Cations. Dalton Trans. 2020 Jul 17;49(27):9495-9504. PubMed PMID: 32608471.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Cooperative N-H bond activation by amido-Ge(ii) cations. AU - Zhou,Xueer, AU - Vasko,Petra, AU - Hicks,Jamie, AU - Fuentes,M Ángeles, AU - Heilmann,Andreas, AU - Kolychev,Eugene L, AU - Aldridge,Simon, PY - 2020/7/2/pubmed PY - 2020/7/2/medline PY - 2020/7/2/entrez SP - 9495 EP - 9504 JF - Dalton transactions (Cambridge, England : 2003) JO - Dalton Trans VL - 49 IS - 27 N2 - N-heterocyclic carbene (NHC) and tertiary phosphine-stabilized germylium-ylidene cations, [R(L)Ge:]+, featuring tethered amido substituents at R have been synthesized via halide abstraction. Characterization in the solid state by X-ray crystallography shows these systems to be monomeric, featuring a two-coordinate C,N- or P,N-ligated germanium atom. The presence of the strongly Lewis acidic cationic germanium centre and proximal amide function allows for facile cleavage of N-H bonds in 1,2-fashion: the products resulting from reactions with carbazole feature a tethered secondary amine donor bound to a three-coordinate carbazolyl-GeII centre. In each case, addition of the components of the N-H bond occurs to the same face of the germanium amide function, consistent with a coordination/proton migration mechanism. Such as sequence is compatible with the idea that substrate coordination via the pπ orbital at germanium reduces the extent of N-to-Ge π donation from the amide, thereby enhancing the basicity of the proximal N-group. SN - 1477-9234 UR - https://www.unboundmedicine.com/medline/citation/32608471/Cooperative_N-H_bond_activation_by_amido-Ge(ii)_cations L2 - https://doi.org/10.1039/d0dt01960g DB - PRIME DP - Unbound Medicine ER -
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