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Lookup NU author(s): Stuart Blair, Dr Keith Izod, Professor William Clegg
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The secondary phosphine R(Me2NCH2-2-C6H4)PH reacts with Bu2Mg to give the homoleptic complex Mg{PR-(C6H4-2-CH2 NMe2)}2 (1) [R = CH(SiMe3)2]. The analogous heavier alkaline earth metal complexes (THF)nAe{PR-(C6H4-2-CH2 NMe2)}2 [Ae = Ca (2), n = 0; Ae = Sr (3), Ba (4), n = 1] have been synthesized by metathesis reactions between K{PR(C6H4-2-CH2NMe2)}and 0.5 equiv of the respective alkaline earth metal diiodide. Compounds 1-4 have been characterized by x-ray crystallography and multielement NMR spectroscopy. In the solid state, compounds 1-4 are monomeric, complexes 1 and 2 adopting a distorted tetrahedral geometry and complexes 3 and 4 adopting a distorted square pyramidal geometry (1: orthorhombic, P212121, a = 11.413(3) Å, b = 12.072(3) Å, c = 32.620(11) Å, Z = 4. 2: monoclinic, P21/c, a = 9.5550(4) Å, b = 17.4560(7) Å, c = 24.5782(10) Å, β = 91.673(2)°, Z = 4. 3: monoclinic, C2/c, a = 15.0498(9) Å, b = 13.0180(8) Å, c = 24.3664(14) Å, β = 104.593(2)°, Z = 4. 4: monoclinic, C2/c, a = 15.2930(10) Å, b = 13.0326(9) Å, c = 24.6491(17) Å, β = 105.542(2)°, Z = 4). In toluene solution, compounds 2-4 are subject to dynamic processes which are attributed to a monomerdimer equilibrium for which bridge-terminal exchange of the phosphanide ligands in the dimer may be frozen out at low temperatures.
Author(s): Blair S, Izod K, Clegg W
Publication type: Article
Publication status: Published
Journal: Inorganic Chemistry
Year: 2002
Volume: 41
Issue: 15
Pages: 3886-3893
ISSN (print): 0020-1669
ISSN (electronic): 1520-510X
Publisher: American Chemical Society
URL: http://dx.doi.org/10.1021/ic0201194
DOI: 10.1021/ic0201194
PubMed id: 12132912
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