SYNTHESIS AND CRYSTAL-STRUCTURE OF CIS-[PD( PH2PCH2C(O)PH )2]-[BF4][B2F7] - UNEXPECTED FORMATION AND 1ST STRUCTURAL CHARACTERIZATION OF THE HEPTAFLUORODIBORATE ANION B2F7-

被引:21
作者
BRAUNSTEIN, P
DOUCE, L
FISCHER, J
CRAIG, NC
GOETZGRANDMONT, G
MATT, D
机构
[1] UNIV STRASBOURG 1,CRISTALLOCHIM & CHIM STRUCT LAB,CNRS,URA 424,F-67070 STRASBOURG,FRANCE
[2] OBERLIN COLL,DEPT CHEM,OBERLIN,OH 44074
[3] ECOLE HAUTES IND CHIM SCI,CHIM MINERALE & ANALYT LAB,CNRS,URA 405,F-67008 STRASBOURG,FRANCE
关键词
D O I
10.1016/S0020-1693(00)82656-0
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of cis-[activated Pd{Ph2PCH = C(O)Ph}2] (1) with HBF4/H2O instantly leads to the formation of the cationic complex cis-[activated Pd{Ph2PCH2C(O)Ph}2][BF4]2. When 1 was treated with commercial BF3.Et2O, containing HBF4 as an impurity, the related compound cis-[activated Pd{Ph2PCH2C(O)Ph}2][BF4][B2F7] (2) was formed. The structure of 2 was determined by an X-ray diffraction study. The compound crystallizes in the orthorhombic system, P2(1)2(1)2(1) space group, Z = 4, cell dimensions: a = 16.474(4), b = 19.007(5), c = 12.932(4) angstrom V = 4049.3 angstrom 3, final R = 0.030. The two chelating phosphines define puckered five membered metallocycles characterised by PCH2 carbon atoms lying significantly out of the metal coordination plane (-0.617(7) angstrom for C1 and +0.779(7) angstrom for C21). This study establishes the first structural data for the B2F7- anion: the value of the B-F(bridge) -B angle is 128.1(7)-degrees. The values of the B-F(bridge) bond lengths (1.50(1) and 1.51(1) angstrom) are significantly longer than the other B-F bonds (1.34-1.39 angstrom).
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页码:151 / 156
页数:6
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