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A Homologous Series of Alkaline Earth Phosphanides: Syntheses, Crystal Structures, and Unusual Dynamic Behavior of (THF)nM[P{CH(Si- Me3)2}(C6H4-2-CH2NMe2)]2 (M = Mg, Ca, Sr, Ba)

Lookup NU author(s): Dr Keith Izod, Emeritus Professor Bill Clegg

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Abstract

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.


Publication metadata

Author(s): Izod K; Clegg W; Blair S

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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