作者:Peter Mu¨ller、Hans Pritzkow、Walter Siebert
DOI:10.1016/s0022-328x(96)06217-1
日期:1996.11
A series of new transitionmetal complexes of 9,10-dihydro-9,10-dimethyl-9,10-diboraanthracene (1) was synthesized and characterized, Mono-, di-, and trinuclear species were isolated, indicating the diversity of the ligand properties of 1. The reaction of 1 with an excess of [CoCp(C2H4)(2)] yields the known 18 VE sandwich complex [(CoCp)1] (2) and the new paramagnetic 32 VE triple-decker complex [(CoCp)(2)1] (3), [RhCp(C2H4)(2)] forms with 1 the 18 VE sandwich complex [(RhCp)1] (4). Two equivalents of [FeCp(C8H12)] and 1 yield the diamagnetic 30 VE triple-decker [(FeCp)(2)1] (5) with the iron atoms eta(6) bifacially coordinated to the heterocycle. The dianion 1(2-) reacts with [CoCp* Br](2) to form [(CoCp*)(3)1] (6) with three independent 18 VE metal centres. The reactions of 1(2-) with [Ni(C3H5)Br](2) and [Ni(C4H7)Br](2) lead to the 30 VE triple-decker complexes [Ni(C3H5)}(2)1] (7a) and [Ni(C4H7)}(2)1] (7b) respectively. [Pd(C8H12)(2)] and [Pt(C8H12)(2)] yield in the reaction with 1 the 18 VE complexes [Pd(C8H12)1] (8) and [Pt(C8H12)1] (9) respectively. The complex [Ni(C6H5)(2)PCH2}(2)1] (10) is generated by reacting 1(2-) with [Ni(C6H5)(2)PCH2}Cl-2(2)]. Two equivalents of the radical anion 1(-) and Ni2+ form the labile 18 VE sandwich [Ni(1)(2)] (11). The constitutions of the new complexes have been derived from spectroscopic data and elemental analyses, and were confirmed by X-ray structure analyses for 5, 6, 7a, 8, 9, and 10.