2009
DOI: 10.1039/b823186a
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Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane

Abstract: Ethynyl- and allenylphosphine-boranes have been prepared by addition at low temperature of borane on the free phosphine. Purification was performed by selective trapping in vacuo and the complexes were characterized by NMR and infrared spectroscopy and mass spectrometry. A kinetic stability lower than that of the corresponding free systems was observed. A series composed of these compounds and methyl-, vinyl-, allyl- and propargylphosphine-boranes was investigated by photoelectron spectroscopy and B3LYP/aug-cc… Show more

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Cited by 9 publications
(15 citation statements)
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“…Hence, one important common feature of these interactions between closed‐shell systems is that the deformation of the interacting subunits usually triggers significant, even dramatic, changes in their chemical properties. This change in chemical properties has been found in the case of many complexes involving BH 3 and some of its derivatives, for which these interactions are particularly strong 1015. The important point we want to emphasize here is that the deformation plays a crucial role when these complexes are formed, so that the strength of the interaction actually can only be correctly rationalized by taking into account the effects that the deformation has on the donor and the acceptor properties of the interacting systems 16.…”
Section: Introductionmentioning
confidence: 68%
“…Hence, one important common feature of these interactions between closed‐shell systems is that the deformation of the interacting subunits usually triggers significant, even dramatic, changes in their chemical properties. This change in chemical properties has been found in the case of many complexes involving BH 3 and some of its derivatives, for which these interactions are particularly strong 1015. The important point we want to emphasize here is that the deformation plays a crucial role when these complexes are formed, so that the strength of the interaction actually can only be correctly rationalized by taking into account the effects that the deformation has on the donor and the acceptor properties of the interacting systems 16.…”
Section: Introductionmentioning
confidence: 68%
“…28 In addition, steric hindrance arising from the peri-geometry is likely to further destabilise the bis(borane) adduct 4c with respect to the monoborane adduct 6. 28 In addition, steric hindrance arising from the peri-geometry is likely to further destabilise the bis(borane) adduct 4c with respect to the monoborane adduct 6.…”
Section: Resultsmentioning
confidence: 99%
“…The unsaturated carbon centres are also heavily deshielded (δ c 137.4 ( J PC 19.0 Hz) C 1 ; 209.9 ( J PC 11.3 Hz) C 2 ), the latter in particular being more characteristic of an allenic, 40 rather than alkynic centre; indeed, these data are in good agreement with those for the limited range of phosphinoallenes § ( Table 2) described previously. 14,41 We thus confidently formulate 15 as (Et 2 N) 2 PC-(Ph)vCvCH 2 (Scheme 2).…”
Section: Formation Of a Phosphino-allenementioning
confidence: 93%