SYNTHESIS AND STRUCTURE OF 1,2-BIS(DIPHENYLPHOSPHINO)ETHANE COMPLEXES OF COPPER(I) ACETATE. CATALYSTS FOR THE DECARBOXYLATION OF CARBOXYLIC ACIDS
SYNTHESIS AND STRUCTURE OF 1,2-BIS(DIPHENYLPHOSPHINO)ETHANE COMPLEXES OF COPPER(I) ACETATE. CATALYSTS FOR THE DECARBOXYLATION OF CARBOXYLIC ACIDS
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乙酸铜 (I) 的 1,2-双（二苯基膦）乙烷配合物的合成和结构。
DOI：
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发表时间：
1994
期刊：
影响因子：
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通讯作者：
J. Reibenspies
中科院分区：
文献类型：
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作者：
D. Darensbourg;E. M. Longridge;B. Khandelwal;J. Reibenspies
合成了几种双齿膦配体与乙酸铜（I）的二聚配合物。这些衍生物之一，dppe（CuO 2CCH 3）2，其中dppe = 1，2-双（二苯基膦基）乙烷，已被确定的固态结构。该络合物以固态存在，作为含有dppe和两个乙酸酯配体的二聚铜（I）单元的聚合物链，通过较弱的Cu-O相互作用将二聚体连接在一起。二聚体单元中的Cu-Cu键长显著长于在乙酸铜（I）中观察到的2.556（2）A，为2.712（2）A。使用这些衍生物作为催化剂前体的氰基乙酸的催化脱羧乙腈和二氧化碳进行了讨论。dppe（CuO_2CCH_3）_2的晶体结构：空间群P_2i/n，a = 14.976（6）A，B = 11.676（3）A，c = 16.999（6）A，β = 107.59（3）°，Z = 4，R = 7.33%
Abstract Several dimeric complexes of copper(I) acetate with bidentate phosphine ligands have been synthesized. The solid-state structure of one of these derivatives, dppe(CuO2CCH3)2, where dppe = 1,2-bis(diphenylphosphino)ethane, has been determined. The complex is shown to exist in the solid-state as a polymeric chain of dimeric copper(I) units containing a dppe and two acetate ligands, with the dimers being linked together via weaker Cu-O interactions. The Cu-Cu bond length in the dimeric units is considerably longer, at 2.712(2) A, than that observed in copper(I) acetate of 2.556(2) A. The use of these derivatives as catalyst precursors for the catalytic decarboxylation of cyanoacetic acid to acetonitrile and carbon dioxide is discussed. Crystal data for dppe(CuO2CCH3)2: space group P2i/n,a = 14.976(6) A, b = 11.676(3) A, c = 16.999(6) A, β = 107.59(3)°, Z = 4, R = 7.33%