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Lookup NU author(s): 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-CH2NMe2)}2 (1) [R = CH(SiMe3)2]. The analogous heavier alkaline earth metal complexes (THF)nAe{PR(C6H4-2-CH2NMe2)}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 multi-element 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), b = 12.072(3), c = 32.620(11) Å, Z = 4. 2: monoclinic, P21/c, a = 9.5550(4), b = 17.4560(7), c = 24.5782(10) Å, = 91.673(2), Z = 4. 3: monoclinic, C2/c, a = 15.0498(9), b = 13.0180(8), c = 24.3664(14) Å, = 104.593(2), Z = 4. 4: monoclinic, C2/c, a = 15.2930(10), b = 13.0326(9), c = 24.6491(17) Å, = 105.542(2), Z = 4). In toluene solution compounds 2 – 4 are subject to dynamic processes which are attributed to a monomer-dimer 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
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