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Synthesis and Structure of [Hg{OP(O)CF 3 (OH)} 2 (PMe 3 ) 3 ], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric Chains
Author(s) -
Pantenburg Ingo,
Thösen Christoph,
Hoge Berthold
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200208)628:8<1785::aid-zaac1785>3.0.co;2-a
Subject(s) - chemistry , trigonal bipyramidal molecular geometry , triclinic crystal system , crystal structure , crystallography , hydrogen bond , trigonal crystal system , stereochemistry , hydrolysis , medicinal chemistry , trifluoromethyl , molecule , organic chemistry , alkyl
The hydrolysis of [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] yields colourless crystals of [Hg{OP(O)CF 3 (OH)} 2 (PMe 3 ) 3 ]. The proposed multistep reaction proceeds via primary hydrolysis of the starting material giving HgO and HP(CF 3 ) 2 . The latter is directly oxidized by HgO to (CF 3 ) 2 P(O)OH. The bis(trifluoromethyl)phosphinic acid hydrolyses to CF 3 P(O)(OH) 2 which reacts with [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] in the presence of PMe 3 to the title compound. The crystal structure was determined by X‐ray single‐crystal analysis (triclinic; P1¯; a = 860.7(1), b = 1007.6(2), c = 1625.0(3) pm; α = 96.09(2), β = 101.09(2), γ = 107.79(2)°; Z = 2) and exhibits distorted trigonal bipyramidal mercury complexes which are connected to polymeric chains. The acidic units, {OP(O)CF 3 (OH)} — , are connected via intermolecular hydrogen bridges, forming two individual centrosymmetric eight membered rings with asymmetric hydrogen bridges with O—O distances of 249.4(8) and 250.8(8) pm.