Sterically encumbered tin and phosphorus peri-substituted acenaphthenes
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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.
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 . DOI: 10.1021/ic5014768
Copyright © 2014 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/ic5014768Copyright © 2014 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1021/ic5014768
The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC), EaStCHEM and the University of St Andrews.