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Boyde NC, Chmely SC, Hanusa TP, et al. Structural distortions in M[E(SiMe₃)₂]₃ complexes (M = group 15, f-element; E = N, CH): is three a crowd?. Inorg Chem. 2014;53(18):9703-14doi: 10.1021/ic501232z.
Boyde, N. C., Chmely, S. C., Hanusa, T. P., Rheingold, A. L., & Brennessel, W. W. (2014). Structural distortions in M[E(SiMe₃)₂]₃ complexes (M = group 15, f-element; E = N, CH): is three a crowd?. Inorganic chemistry, 53(18), 9703-14. https://doi.org/10.1021/ic501232z
Boyde, Nicholas C, et al. "Structural distortions in M[E(SiMe₃)₂]₃ complexes (M = group 15, f-element; E = N, CH): is three a crowd?." Inorganic chemistry vol. 53,18 (2014): 9703-14. doi: https://doi.org/10.1021/ic501232z
Boyde NC, Chmely SC, Hanusa TP, Rheingold AL, Brennessel WW. Structural distortions in M[E(SiMe₃)₂]₃ complexes (M = group 15, f-element; E = N, CH): is three a crowd?. Inorg Chem. 2014 Sep 15;53(18):9703-14. doi: 10.1021/ic501232z. Epub 2014 Aug 29. PMID: 25171144.
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Inorg Chem. 2014 Sep 15;53(18):9703-14. doi: 10.1021/ic501232z. Epub 2014 Aug 29.

Structural distortions in M[E(SiMe₃)₂]₃ complexes (M = group 15, f-element; E = N, CH): is three a crowd?.

Inorganic chemistry

Nicholas C Boyde, Stephen C Chmely, Timothy P Hanusa, Arnold L Rheingold, William W Brennessel

Affiliations

  1. Department of Chemistry, Vanderbilt University , Nashville, Tennessee 37235, United States.

PMID: 25171144 DOI: 10.1021/ic501232z

Abstract

The tris(bistrimethylsilylamido) species P[N(SiMe3)2]3 (1) and As[N(SiMe3)2]3 (2) have been prepared through halide metathesis in high yield. Their single crystal X-ray structures, along with that of Sb[N(SiMe3)2]3 (3), complete the series of structurally authenticated group 15 M[N(SiMe3)2]3 complexes (the bismuth analogue (4) has been previously reported). All four complexes possess the expected pyramidal geometries, with progressively longer M-N bond distances from P to Bi but closely similar N-M-N angles (107-104°). The structures of 1-4 also display distortions that are similar to those in f-element M[N(SiMe3)2]3 and M[CH(SiMe3)2]3 complexes, in which M···(β-Si-C) interactions have been identified. Such structural features include distorted M-(N,CH)-Si and (N,CH)-Si-C angles and close M···C and M···Si contacts. DFT calculations confirm that there are no M···(β-Si-C) interactions in 1-4; the bond distortions appear to result from the particular steric crowding that arises in pyramidal M[(N,CH)(SiMe3)2]3 complexes. This is likely the source of the most of the distortions in the structures of the f-element analogues as well, even though the latter possess attractive M···Si-C interactions.

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