Zusammenfassung
By using [(CpCo)(2)tol] (Cp = (5)-C(5)H(2)tBu(3), tol = toluene), a new synthesis of the 1,3-diphosphete complexes [CpCo((4)-P(2)C(2)tBu(2))] (1a) and [CpCo((4)-P(2)C(2)iPr(2))] (1b) was found, and their reactions with the Lewis acids W(CO)(4) and Cu-I halides were investigated. The reaction of 1b with W(CO)(4)(nbd) (nbd = norbornadiene) leads to the complex [(CpCo)(,(4:1)-{PCiPr}(2))](2)W(CO)(4) ...
Zusammenfassung
By using [(CpCo)(2)tol] (Cp = (5)-C(5)H(2)tBu(3), tol = toluene), a new synthesis of the 1,3-diphosphete complexes [CpCo((4)-P(2)C(2)tBu(2))] (1a) and [CpCo((4)-P(2)C(2)iPr(2))] (1b) was found, and their reactions with the Lewis acids W(CO)(4) and Cu-I halides were investigated. The reaction of 1b with W(CO)(4)(nbd) (nbd = norbornadiene) leads to the complex [(CpCo)(,(4:1)-{PCiPr}(2))](2)W(CO)(4) (2) with the two diphosphete complexes 1b coordinated trans to a central W(CO)(4) moiety. The reactions of 1a with Cu-I halides result in different products depending on the stoichiometry. In a 1:1 ratio, the dimeric compounds 3a-c [(CpCo)(,(4:1)-{PCtBu}(2))Cu(-X)](2) (3a: X = Cl; 3b: X = Br, 3c: X = I) were isolated, whereas an excess of CuX gave the two-dimensional polymers [({CpCo}{(3),(4:1:1)-(PCtBu)(2)})(2)(Cu{(3)-X})(4)](n) (6a: X = Cl, 6b: X = Br, 6c: X = I). From the reaction of 1a and 1b with CuBr and CuI in a 1:2 or 2:3 ratio, the one-dimensional polymers [({CpCo}{(3),(4:1:1)-(PCR)(2)})({CpCo}{,(4:1)-(PCR)(2)})(Cu{(3)-X})(4)](n) (4a: X = Br, R = iPr, 4b: X = I, R = iPr, 4c: X = I, R = tBu) are formed. From the reaction of 1a with CuI, a second product, [({CpCo}{(3),(4:1:1)-(PCtBu)(2)})(Cu{(3)-I})(4)(MeCN)(2)](n) (5), was isolated by using CH3CN for crystallization. The products were comprehensively characterized by spectroscopic methods, X-ray crystallography, and P-31 magic angle spinning (MAS) NMR spectroscopy.
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