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

Content Provider	Semantic Scholar
Author	Izod, Keith Wills, Corinne El-Hamruni, Salima M. Harrington, Ross W. Waddell, Paul Probert, Michael R.
Copyright Year	2015
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,...
Starting Page	2406
Ending Page	2414
Page Count	9
File Format	PDF HTM / HTML
DOI	10.1021/om501183p
Alternate Webpage(s)	https://eprint.ncl.ac.uk/file_store/production/210830/CBCDD96B-E011-4750-9D85-A01A062F746A.pdf
Alternate Webpage(s)	https://doi.org/10.1021/om501183p
Volume Number	34
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article