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Structural Diversity in Alkaline Earth Metal Complexes of a Phosphine-Borane-Stabilized 1,3-Dicarbanion

Lookup NU author(s): Dr Keith IzodORCiD, Dr Corinne Wills, Salima El-Hamruni, Dr Ross Harrington, Dr Paul Waddell, Professor Mike ProbertORCiD

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Abstract

The reaction between (4-tBuC₆H₄CH₂)₂Ca and one equivalent of PhP(BH₃)(CH₂SiMe₃)₂ (1) in diethyl ether gives the dimeric complex [[PhP(BH₃){CH(SiMe₃)}₂]Ca(OEt₂)]₂ (2) in good yield. Similar reactions between 1 and one equivalent of either (PhCH₂)₂Sr(THF) or (PhCH₂)₂Ba yield the corresponding dimers [[PhP(BH₃){CH(SiMe₃)}₂]Sr(THF)_1.75(OEt₂)_0.25]₂ (3) and [[PhP(BH₃){CH(SiMe₃)}₂]Ba(OEt₂)_1.75(THF)_0.25]₂ (4), respectively. Unexpectedly, an attempt to prepare 3 from a one-pot reaction between SrI₂, 1 and two equivalents of PhCH₂K gave the complex [[PhP(BH₃){CH(SiMe₃)}₂]₂Sr₃K₂(OEt₂)(THF)₂]₂.Et₂O (5) in low yield. While superficially similar, compounds 2, 3 and 4 crystallize with distinct structures, which differ either in the chirality of the carbanion centers, or in the nature of the bridging group. Compounds 2, 3 and 4 decompose slowly in THF solution to give ethylene, Ae(OEt)₂ (or Ae(OCH=CH₂)₂) and the monocarbanion derivatives [PhP(BH₃){CH(SiMe₃)}{CH₂SiMe₃}]₂Ae(THF)_n, according to NMR spectroscopy [Ae = Ca, Sr, Ba].

Publication metadata

Author(s): Izod K, Wills C, El-Hamruni S, Harrington RW, Waddell PG, Probert MR

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2015

Volume: 34

Issue: 11

Pages: 2406-2414

Print publication date: 08/06/2015

Online publication date: 27/02/2015

Acceptance date: 23/02/2015

Date deposited: 23/02/2015

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/om501183p

DOI: 10.1021/om501183p

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