Toggle Main Menu Toggle Search

Open Access padlockePrints

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): Stuart Blair, Dr Keith Izod, Emeritus Professor Bill Clegg

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

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.


Publication metadata

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


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share