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Sterically encumbered tin and phosphorus peri-substituted acenaphthenes
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dc.contributor.author | Chalmers, Brian Alexander | |
dc.contributor.author | Athukorala Arachchige, Kasun Sankalpa | |
dc.contributor.author | Prentis, Joanna | |
dc.contributor.author | Knight, Fergus Ross | |
dc.contributor.author | Kilian, Petr | |
dc.contributor.author | Slawin, Alexandra Martha Zoya | |
dc.contributor.author | Woollins, J Derek | |
dc.date.accessioned | 2016-04-01T12:00:05Z | |
dc.date.available | 2016-04-01T12:00:05Z | |
dc.date.issued | 2014-07-31 | |
dc.identifier | 192592823 | |
dc.identifier | d85a972b-171a-4147-ba8d-cc9fb96b8747 | |
dc.identifier | 84906278382 | |
dc.identifier | 000340576900066 | |
dc.identifier.citation | Chalmers , B A , Athukorala Arachchige , K S , Prentis , J , Knight , F R , Kilian , P , Slawin , A M Z & Woollins , J D 2014 , ' Sterically encumbered tin and phosphorus peri -substituted acenaphthenes ' , Inorganic Chemistry , vol. 53 , no. 16 , pp. 8795-8808 . https://doi.org/10.1021/ic5014768 | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.other | ORCID: /0000-0002-2999-2272/work/55901236 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/56862027 | |
dc.identifier.other | ORCID: /0000-0001-6379-3026/work/58285420 | |
dc.identifier.other | ORCID: /0000-0002-1498-9652/work/31779193 | |
dc.identifier.uri | https://hdl.handle.net/10023/8535 | |
dc.description | The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC), EaStCHEM and the University of St Andrews. | en |
dc.description.abstract | A group of sterically encumbered peri-substituted acenaphthenes have been prepared, containing tin moieties at the 5,6-positions in 1 – 3 ([Acenap(SnR3)2], Acenap = acenaphthene-5,6-diyl; R3 = Ph3 ( 1 ), Me3 ( 2 ); [(Acenap)2(SnMe2)2] ( 3 )) and phosphorus functional groups at the proximal peri-positions in 4 and 5 ([Acenap(PR2)(PiPr2)] R2 = Ph2 ( 4 ), Ph(iPr) ( 5 )). Bis(stannane) structures 1 – 3 are dominated by repulsive interactions between the bulky tin groups, leading to peri-distances approaching the sum of van der Waals radii. Conversely, the quasi-linear CPh-P···P three-body fragments found in bis(phosphine) 4 suggest the presence of a lp(P)−σ*(P–C) donor–acceptor 3c-4e type interaction, supported by a notably short intramolecular P···P distance and notably large JPP through-space coupling (180 Hz). Severely strained bis(sulfides) 4-S and 5-S , experiencing pronounced in-plane and out-of-plane displacements of the exocyclic peri-bonds, have also been isolated following treatment of 4 and 5 with sulfur. The resulting nonbonded intramolecular P···P distances, ∼4.05 Å and ∼12% longer than twice the van der Waals radii of P (3.60 Å), are among the largest ever reported peri-separations, independent of the heteroatoms involved, and comparable to the distance found in 1 containing the larger Sn atoms (4.07 Å). In addition we report two metal complexes with square planar [( 4 )PtCl2] ( 4-Pt ) and octahedral cis-[( 4 )Mo(CO)4] ( 4-Mo ) geometries. In both complexes the bis(phosphine) backbone is distorted, but notably less so than in bis(sulfide) 4-S . All compounds were fully characterized, and except for bis(phosphine) 5 , crystal structures were determined. | |
dc.format.extent | 14 | |
dc.format.extent | 1885170 | |
dc.format.extent | 631488 | |
dc.language.iso | eng | |
dc.relation.ispartof | Inorganic Chemistry | en |
dc.subject | QD Chemistry | en |
dc.subject.lcc | QD | en |
dc.title | Sterically encumbered tin and phosphorus peri-substituted acenaphthenes | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. Office of the Principal | en |
dc.identifier.doi | 10.1021/ic5014768 | |
dc.description.status | Peer reviewed | en |
dc.identifier.url | http://pubs.acs.org/doi/suppl/10.1021/ic5014768 | en |
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