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Bimetallic Complexes with Conjugated C<sub>4</sub>, C<sub>6</sub>, C<sub>10</sub>, and C<sub>14</sub> Bridges :  Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes

Bimetallic Complexes with Conjugated C4, C6, C10, and C14 Bridges :  Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes

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HARTBAUM, Cornelia, Elvira MAUZ, Gerhard ROTH, Kerstin WEISSENBACH, Helmut FISCHER, 1999. Bimetallic Complexes with Conjugated C4, C6, C10, and C14 Bridges :  Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes. In: Organometallics. 18(14), pp. 2619-2627. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om990145i

@article{Hartbaum1999Bimet-23038, title={Bimetallic Complexes with Conjugated C4, C6, C10, and C14 Bridges :  Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes}, year={1999}, doi={10.1021/om990145i}, number={14}, volume={18}, issn={0276-7333}, journal={Organometallics}, pages={2619--2627}, author={Hartbaum, Cornelia and Mauz, Elvira and Roth, Gerhard and Weissenbach, Kerstin and Fischer, Helmut} }

Fischer, Helmut Weissenbach, Kerstin Organometallics ; 18 (1999), 14. - S. 2619–2627 Bimetallic Complexes with Conjugated C<sub>4</sub>, C<sub>6</sub>, C<sub>10</sub>, and C<sub>14</sub> Bridges :  Synthetic Routes to Alkynediyl-Bridged Bis(carbene) Complexes Roth, Gerhard The reaction of [(CO)5WC(Ph)H] with Me2NCCNMe2 affords two complexes:  the binuclear complex [(CO)5WC(NMe2)(Me2N)CW(CO)5] (2) and the insertion product [(CO)5WC(NMe2)C(NMe2)C(Ph)H] (3). Sequential reaction of the (dimethylamino)ethynylcarbene complex [(CO)5WC(NMe2)CCH] (4a) with nBuLi, W(CO)6, and F3CSO3Me yields the new ethynediyl-bridged binuclear alkoxycarbene−aminocarbene complex [(CO)5WC(NMe2)CC(MeO)CW(CO)5] (5). Treatment of 4a and of [(CO)5CrC(NMe2)CCH] (4b) with nBuLi and iodine gives the new iodine-substituted complexes [(CO)5MC(NMe2)CCI] (M = W (6a), M = Cr (6b)). By Pd-catalyzed coupling of 6a,b with the C-stannylated ethynylcarbene complexes [(CO)5MC(NMe2)CCSn(nBu)3] (7a,b) the butadiynediyl-bridged bis(carbene) complexes [(CO)5MC(NMe2)(CC)2(Me2N)CM(CO)5] (8a,b) are obtained. Analogously, from [(CO)5WC(NMe2)(CC)xH] (x = 2, 3) and nBuLi/I2 amino(iodobutadiynyl)carbene and amino(iodohexatriynyl)carbene complexes [(CO)5WC(NMe2)(CC)xI] (x = 2 (10), 3 (14)) are obtained. Pd-catalyzed coupling with the corresponding C-stannylated alkynylcarbene complexes finally affords the binuclear C10(NMe2)2- and C14(NMe2)2-bridged complexes [(CO)5WC(NMe2)(CC)x(Me2N)CW(CO)5] (x = 4 (12), 6 (16)). All alkynediyl-bridged bis(carbene) complexes are stable at room temperature. The spectroscopic data of 5 indicate that it is best described as a hybrid of a dipolar allenyl-type compound and an alkynylcarbene complex. In contrast, the CC units in the binuclear complexes 8a,b, 12, and 16 are essentially localized. Roth, Gerhard 2013-06-12T07:48:02Z Weissenbach, Kerstin 1999 Fischer, Helmut Hartbaum, Cornelia Mauz, Elvira deposit-license eng Mauz, Elvira Hartbaum, Cornelia 2013-06-12T07:48:02Z

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