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Structural studies of uranyl complexes of diphenyl-dimethylaminosulfonylmethyl phosphine oxide and diisopropyl-tolylsulfinylmethyl phosphonate ligands

Authors
Journal
Inorganica Chimica Acta
0020-1693
Publisher
Elsevier
Publication Date
Volume
172
Issue
2
Identifiers
DOI: 10.1016/s0020-1693(00)80852-x

Abstract

Abstract The molecular structures of the bifunctional ligand, (C 6H 5) 2P(O)CH 2S(O) 2N(CH 3) 2 ( 1), and its coordination complex, UO 2(NO 3) 2 [(C 6H 5) 2P(O)CH 2- S(O) 2N(CH 3) 2] 2 ( 2), were determined by single crystal X-ray diffraction techniques, and the structural influences on the ligand due to coordination were examined. The ligand 1 crystallizes in the monoclinic space group Cc, with a = 15.982(3), b = 10.003(2), c = 10.245(3) Å, β = 99.47(2)°, Z = 4 and V = 1615.5 Å 3, R F = 2.8% on 1158 unique reflections ( I ≥ 2σ( I)). Complex 2 is found in the monoclinic space group P2 1/ c, with a = 12.680(3), b = 16.149(5), c = 20.204(6) Å, β = 107.17(2), Z = 4 and V = 3952.7 Å 3, R F = 5.2% on 5060 unique reflections ( I ≥ 2σ( I)). The complex contains two phosphine oxide ligands bonded to the uranium atom through the phosphoryl oxygen atoms in a trans orientation with UO(P) 2.35(1) Å. The molecular structure for the sulfinylmethylphosphonate complex, UO 2(NO 3) 2 [(i-C 3H 7O) 2 P(O)CH 2 S(O)( p-CH 3C 6H 4)] ( 3), was also determined by single crystal X-ray diffraction techniques, and it crystallized in the monoclinic space group P2 1/ c, with a = 10.759- (8), b = 13.811(3), c = 17.823(5) Å, β = 105.83(3)°, Z = 4 and V = 2548 Å 3, R F = 10.9% on 1908 unique reflections ( I ≥ 2σ( I)). The complex shows a single ligand bonded in a bidentate mode to the uranium atom with UO(P) 2.37(2) Å and UO(S) 2.36(2) Å.

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