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1 2013

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Addition of boranes to (E)-(η5-C5H5)2Zr(CH=CHPh)Cl

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Ferland P. , Prosser K. , Bourque J. , Edwards I. , Hamilton N. , Joyce L. , Finniss M. , Yorke S. , Vogels C. , Fontaine F.-G. , Decken A. , Westcott S.

Open Chemistry

2013

tom 11

nr 5

811-816

In this study, the addition of boranes to (E)-(η5-C5H5)2Zr(CH=CHPh)Cl (3) has been examined in order to investigate the regioselectivity of these ‘hydroboration’ reactions. We have found that these additions proceed with remarkable selectivity to give exclusive formation of a saturated organic molecule where one carbon atom has both the boron and the zirconium fragments. These reactions do not proceed via a conventional hydroboration reaction, but instead go through an initial transmetalation step to generate (E)-(η5-C5H5)2Zr(H)Cl (1) and the corresponding alkenyl boron intermediate, whereupon subsequent hydrozirconation of this latter species gives the geminal products. An x-ray diffraction study has been conducted on gem-(η5-C5H5)2Zr(CH(Bpin)CH2Ph)Cl (pin = 1, 2-O2C2Me4) (2). Crystals of 2 were orthorhombic with a = 18.545(3) Å, b = 15.713(3) Å, c = 16.157(3) Å in the space group Pccn. An x-ray diffraction study has also been conducted on the trinuclear zirconium oxide species (η5-C5H5)2ZrO2[ZrCl(η5-C5H5)2]2(4). Crystals of 4 were orthorhombic with a = 13.6000(8) Å, b = 14.2252(8) Å, c = 17.6500(10) Å in the space group P2(1)2(1)2(1). [...]