Additions and intramolecular migrations of nucleophiles in cationic diruthenium mu-allenyl complexes

作者：Knox Selby A R; Marchetti Fabio^*

来源：Journal of Organometallic Chemistry, 2007, 692(19): 4119-4128.

DOI：10.1016/j.jorganchem.2007.06.029

• diruthenium complexes
• allenyl
• bridging vinyl-chlorocarbene
• bridging hydride
• hydride migration

The diruthenium mu-allenyl complex [Ru-2(CO)(NCMe)([mu-CO)[mu-eta(1):eta(2)-C(H)=C=C(Me)(Ph)}(CP)(2)][BF4], 3b, reacts with halide anions to yield the neutral derivatives [Ru-2(CO)(2)(X) {mu-eta(1):eta(2)-C(H)=C=C(Me)(Ph)} (CP)(2)] [X = Cl, 4b; X = Br, 4c; X = 1, 4d]. Complex 4b undergoes isomerization to the unprecedented bridging vinyl-chlorocarbene species [Ru-2(CO)(mu-CO){mu-eta(1):eta(3)-C(Cl)C(H)= C(Me)(Ph))(CP)21, 10, upon filtration of a CH2Cl2 solution through an alumina column.
Complex 3b reacts with an excess of NaBH4 to give five products: the allene complex [Ru-2(CO)(mu-H){mu-eta(2):eta(2)-CH2=C= C(Me)(Ph))(CP)(2)], 5; the hydride species trans-[Ru-2(CO)(2)(mu-H){mu-eta(1):eta(2)-CH=C=C(Me)(Ph)1(CP)2], 6, and cis-[Ru-2(CO)(2)(mu-H){mu- eta(1):eta(2) -CH=C=C(Me)(Ph)}1(CP)(2)], 8; the vinyl-alkylidene [Ru-2(CO)(mu-CO){mu-eta(1):eta(3)-C(H)C(H)=C(NIe)(Ph)}(CP)21, 9; and the cluster [Ru-3(CO)(3)(mu-H)(3)(Cp)(3)], 7.
Studies on the thermal stabilities of 5, 6, 8 and 9 have suggested a plausible mechanism for the formation of these complexes and for the synthesis of 10.

• 出版日期2007-9-1