The impact of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane, P(OCH2)2(OCCH3) (1 ) as a ligand for Ru(II) catalyzed hydroarylation of olefins was studied. The complexes TpRu(L)(PPh3)Cl [Tp = hydridotris(pyrazolyl)borate; L = 1 , P(OCH2)3CEt, PMe3 or P(OMe)3], (h6-C6H6)Ru(L)Cl2 [ L = 1 , PPh3, P(OMe)3, PMe3, P(OCH2)3CEt or CO] and (h6-p-cymene)Ru(L)Cl2 [L = 1 , P(OCH2)3CEt, P(OMe)3, or PPh3] were synthesized, isolated and characterized by NMR spectroscopy, cyclic voltammetry, mass spectrometry and, for some complexes, single crystal X-ray diffraction. Data from cyclic voltammetry and solid-state structures were used to compare the properties of 1  with other phosphorus-based ligands and carbon monoxide. For the Ru(II) complexes studied, these data are consistent with the overall donor ability of 1  being less than other common phosphines and phosphites but greater than carbon monoxide. To further gain an understanding of the effects of 1  on catalytic hydroarylation,  TpRu[P(OCH2)2(OCCH3)](NCCH3)Ph was isolated. TpRu[P(OCH2)2(OCCH3)](NCCH3)Ph catalyzes hydrophenylation of ethylene up to ~60 turnovers of ethylbenzene.

Preparation of Ru(II) complexes with the strained phosphite (4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1] heptane): Comparison to related phosphine systems and development of a catalyst for olefin hydroarylation

244th National Meeting (2012)

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