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Synthesis, spectroscopic and structural properties of an unusual series of homoleptic phosphine oxide complexes of the alkaline earth dications

Synthesis, spectroscopic and structural properties of an unusual series of homoleptic phosphine oxide complexes of the alkaline earth dications
Synthesis, spectroscopic and structural properties of an unusual series of homoleptic phosphine oxide complexes of the alkaline earth dications
The distorted tetrahedral [M(OPPh3)(4)](SbCl6)(2) (M = Mg, Ca, Sr) are obtained from MCl2, OPPh3 and SbCl3 in suitable solvent conditions, while Ba2+ gives [Ba(OPPh3)(5)](SbCl6)(2). The chelating o-C6H4(P(O)Ph-2)(2) gives the tris complexes [M{o-C6H4(P(O)Ph-2)(2)}(3)](SbCl6)(2), while under similar conditions the stoichiometries of the products obtained using Ph2P(O)CH2P(O)Ph-2 vary, with M; and products include the five-coordinate [Mg{Ph2P(O)CH2P(O)Ph-2}(2)(H2O)](SbCl6)(2), the distorted octahedral [M{Ph2P(O)CH2P(O)Ph-2}(3)](SbCl6)(2) (M = Ca or Sr) and the seven-coordinate [Sr{Ph2P(O)CH2P(O)Ph-2}(3)(EtOH)](SbCl6)(2). Strontium is unusual in that both six- and seven-coordinate species are evident and may be isolated depending upon the reaction conditions. These are the first reported Group 2 complexes with bidentate phosphine oxides and there are no other phosphine oxide complexes with Sr or Ba. Crystal structures are reported for {Mg(OPPh3)(4)](SbCl6) (2).CH2Cl2 [Ca{Ph2P(O)CH2P(O)Ph-2}(3)] (SbCl6)(2).2CH(2)Cl(2) and [Sr{Ph2P(O)CH2P(O)Ph-2}(3)(EtOH)](SbCl6)(2).0.45CH(2)Cl(2). The compounds isolated show significant dependence upon the charge:radius ratio of the metal and the steric bulk and rigidity of the ligand.
homoleptic phosphine oxide complexes, alkaline earth dications, multinuclear nmr, oxide, magnesium(ii) perchlorate, triphenylphosphineoxide, crystal-structure, halide-complexes, arsine oxides, yttrium, scandium, xylyl
0277-5387
121-128
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Levason, Wiliiam
414316d1-419c-41a0-bad6-c301cccc8ed4
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Stainer, Holly
73360784-71b2-4913-b184-eb86e47ce616
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Levason, Wiliiam
414316d1-419c-41a0-bad6-c301cccc8ed4
Ratnani, Raju
0a86c56f-00c6-4c9f-8aa0-52667938ba70
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Stainer, Holly
73360784-71b2-4913-b184-eb86e47ce616
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Hursthouse, Michael B., Levason, Wiliiam, Ratnani, Raju, Reid, Gillian, Stainer, Holly and Webster, Michael (2005) Synthesis, spectroscopic and structural properties of an unusual series of homoleptic phosphine oxide complexes of the alkaline earth dications. Polyhedron, 24 (1), 121-128. (doi:10.1016/j.poly.2004.10.009).

Record type: Article

Abstract

The distorted tetrahedral [M(OPPh3)(4)](SbCl6)(2) (M = Mg, Ca, Sr) are obtained from MCl2, OPPh3 and SbCl3 in suitable solvent conditions, while Ba2+ gives [Ba(OPPh3)(5)](SbCl6)(2). The chelating o-C6H4(P(O)Ph-2)(2) gives the tris complexes [M{o-C6H4(P(O)Ph-2)(2)}(3)](SbCl6)(2), while under similar conditions the stoichiometries of the products obtained using Ph2P(O)CH2P(O)Ph-2 vary, with M; and products include the five-coordinate [Mg{Ph2P(O)CH2P(O)Ph-2}(2)(H2O)](SbCl6)(2), the distorted octahedral [M{Ph2P(O)CH2P(O)Ph-2}(3)](SbCl6)(2) (M = Ca or Sr) and the seven-coordinate [Sr{Ph2P(O)CH2P(O)Ph-2}(3)(EtOH)](SbCl6)(2). Strontium is unusual in that both six- and seven-coordinate species are evident and may be isolated depending upon the reaction conditions. These are the first reported Group 2 complexes with bidentate phosphine oxides and there are no other phosphine oxide complexes with Sr or Ba. Crystal structures are reported for {Mg(OPPh3)(4)](SbCl6) (2).CH2Cl2 [Ca{Ph2P(O)CH2P(O)Ph-2}(3)] (SbCl6)(2).2CH(2)Cl(2) and [Sr{Ph2P(O)CH2P(O)Ph-2}(3)(EtOH)](SbCl6)(2).0.45CH(2)Cl(2). The compounds isolated show significant dependence upon the charge:radius ratio of the metal and the steric bulk and rigidity of the ligand.

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More information

Published date: 6 January 2005
Keywords: homoleptic phosphine oxide complexes, alkaline earth dications, multinuclear nmr, oxide, magnesium(ii) perchlorate, triphenylphosphineoxide, crystal-structure, halide-complexes, arsine oxides, yttrium, scandium, xylyl

Identifiers

Local EPrints ID: 20831
URI: http://eprints.soton.ac.uk/id/eprint/20831
ISSN: 0277-5387
PURE UUID: 71144d3e-b30f-4084-9583-4b4bd10e2d34
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 02 Mar 2006
Last modified: 07 Oct 2020 01:36

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Contributors

Author: Michael B. Hursthouse
Author: Wiliiam Levason
Author: Raju Ratnani
Author: Gillian Reid ORCID iD
Author: Holly Stainer
Author: Michael Webster

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