Binuclear ?- and η3-Benzylic Derivatives of Nickel

Article abstract of DOI:10.1039/DT9920001769

The stepwise reaction of the dibromides m- and p-BrC6H4Br with (cod = cycloocta-1,5-diene) affords the ?-benzylic derivatives trans- 1a (meta) or 1b (para) and the binuclear species trans,trans-<(Me3P)2BrNi(μ-?:?-CH2C6H4)NiBr(PMe3)2> 2a (meta) or 2b (para).If the second oxidative addition is carried out using equimolar amounts of and PMe3 the pseudo-allyl complexes trans-<(Me3)BrNi(μ-η³:?-CH2C6H4)NiBr(PMe3)2> 5a (meta) or 5b (para) are obtained instead.Carbonylation of the binuclear compounds 2 yields the stable bis(acyl) derivatives trans,trans-<(Me3P)2BrNi(μ-COCH2C6H4CO)NiBr(PMe3)2> 3a (meta) or 3b (para) while excess of PMe3 induces a reductive elimination process that furnishes the bis(aryl) species trans,trans-<(Me3P)2BrNi(μ-C6H4CH2CH2C6H4)NiBr(PMe3)2> 4a (meta) or 4b (para).A crystal structure determination of complex 2b has been undertaken: monoclinic, space group P2₁/c, with cell dimensions a = 11.241(1), b = 8.866(2), c = 29.323(8) Angstroem, β = 90.22(1) grad and Z = 4.The geometry around both nickel atoms is distorted square planar, with a dihedral angle between the two co-ordination planes of 103.77(9) grad.

Full text of DOI:10.1039/DT9920001769

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