SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE ALKALINE-EARTH ARYLOXIDE AGGREGATES H2BA8(MU-5-O)2(OPH)14(HMPA)6 AND H2SR6BA2(MU-5-O)2(OPH)14(HMPA)6 - A NEW STRUCTURAL TYPE DISPLAYING METAL-ION SITE SELECTIVITY

被引:35
作者
CAULTON, KG [1 ]
CHISHOLM, MH [1 ]
DRAKE, SR [1 ]
FOLTING, K [1 ]
HUFFMAN, JC [1 ]
机构
[1] INDIANA UNIV,CTR MOLEC STRUCT,BLOOMINGTON,IN 47405
关键词
D O I
10.1021/ic00058a011
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of barium metal granules with phenol and hexamethylphosphoramide (HMPA) in toluene at 25-degrees-C yields a novel eight-metal atom aggregate. The reaction of Sr3(OPh)6(HMPA)5 with barium metal and phenol yields a structurally related species. The two aggregates have been characterized by IR and H-1, C-13, and P-31{H-1} NMR spectroscopy and single-crystal X-ray studies and shown to consist to two square-based pyramidal M5(mu5-O) fragments sharing a common basal edge. The structure is completed by mu3- and mu2-phenoxide and terminal HMPA ligands. The selectivity for barium in the two polyhedral sites where the square-based pyramids are joined originates in the higher coordination number there. Crystal data: for H2Ba8O2(OPh)14(HMPA)6.2PhMe (-172-degrees-C), a = 16.379(3) angstrom, b = 19.504(4) angstrom, c = 26.763(5) angstrom, beta = 100.90(0)-degrees with Z = 2 in space group P2(1)/n; for H2Sr6-Ba2O2(OPh) 14(HMPA)6.2PhMe (-158-degrees-C), a = 17.797(2) angstrom, b = 17.421(2) angstrom, c = 26.624(3) angstrom, beta = 107.62(0)-degrees with Z = 2 in space group P2(1)/n.
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页码:816 / 820
页数:5
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