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Synthesis spectroscopic and structural properties of transition metal complexes of the o-xylyl diphosphine o-C6H4(CH2PPh2)2

Synthesis spectroscopic and structural properties of transition metal complexes of the o-xylyl diphosphine o-C6H4(CH2PPh2)2
Synthesis spectroscopic and structural properties of transition metal complexes of the o-xylyl diphosphine o-C6H4(CH2PPh2)2
The systematic coordination chemistry of the wide-angle diphosphine o-C6H4(CH2PPh2)2 (L1) has been investigated with metal ions from Groups 9–11 in order to explore the consequences of the steric demands of the phosphine and its flexibility towards different oxidation states and coordination geometries. The products isolated include the tetrahedral [CoX2(L1)] (X = Cl, Br or I), the very distorted square planar [Rh(L1)2]+, [M(cod)(L1)]+ (M = Rh or Ir), square planar [NiX2(L1)] (X = Cl or Br), [M?Cl2(L1)] (M? = Pd or Pt), the chloro-bridged [Pd2Cl2(L1)2]2+, [Pd(L1)2]2+, the tetrahedral [M?(L1)2]+ (M? = Cu, Ag or Au) and the dinuclear [(AuCl)2(L1)]. Chemical oxidation of some of the complexes are described, giving examples of Co(III), Ni(III) and Pt(IV) species. Where possible the products have been characterised by IR, UV–vis, NMR (1H, 31P, 63Cu and 195Pt as appropriate) spectroscopies, mass spectrometry and microanalysis. Crystal structures of six representative examples confirm the coordination environments in particular species and illustrate the steric demands of L1. L1 is a versatile ligand which can readily alter its chelate bite angle to accommodate a range of coordination geometries (the P…P distances within the chelate rings varies by >0.5 Å), and the presence of the rigid aromatic ring in the C4 backbone leads to some preorganisation favouring cis chelation. It also shows a preference for low coordination numbers and this results in some unexpected products.
diphosphine, metal complexes, x-ray structures, higher oxidation-states, bidentate phosphine-ligands, multi-dentatephosphorus, coordination chemistry, bi-dentate, rhodium(iii) complexes, crystal-structures, carbon sulfides, platinum(ii), palladium(ii)
0277-5387
75-87
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
1aee0faa-cd59-4d06-bb7a-9a25a0a561ab
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Watts, Rebecca
12448434-76ca-4078-a3da-7f3485affa80
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
1aee0faa-cd59-4d06-bb7a-9a25a0a561ab
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Watts, Rebecca
12448434-76ca-4078-a3da-7f3485affa80

Brown, Michael D., Levason, William, Reid, Gillian and Watts, Rebecca (2005) Synthesis spectroscopic and structural properties of transition metal complexes of the o-xylyl diphosphine o-C6H4(CH2PPh2)2. Polyhedron, 24 (1), 75-87. (doi:10.1016/j.poly.2004.10.008).

Record type: Article

Abstract

The systematic coordination chemistry of the wide-angle diphosphine o-C6H4(CH2PPh2)2 (L1) has been investigated with metal ions from Groups 9–11 in order to explore the consequences of the steric demands of the phosphine and its flexibility towards different oxidation states and coordination geometries. The products isolated include the tetrahedral [CoX2(L1)] (X = Cl, Br or I), the very distorted square planar [Rh(L1)2]+, [M(cod)(L1)]+ (M = Rh or Ir), square planar [NiX2(L1)] (X = Cl or Br), [M?Cl2(L1)] (M? = Pd or Pt), the chloro-bridged [Pd2Cl2(L1)2]2+, [Pd(L1)2]2+, the tetrahedral [M?(L1)2]+ (M? = Cu, Ag or Au) and the dinuclear [(AuCl)2(L1)]. Chemical oxidation of some of the complexes are described, giving examples of Co(III), Ni(III) and Pt(IV) species. Where possible the products have been characterised by IR, UV–vis, NMR (1H, 31P, 63Cu and 195Pt as appropriate) spectroscopies, mass spectrometry and microanalysis. Crystal structures of six representative examples confirm the coordination environments in particular species and illustrate the steric demands of L1. L1 is a versatile ligand which can readily alter its chelate bite angle to accommodate a range of coordination geometries (the P…P distances within the chelate rings varies by >0.5 Å), and the presence of the rigid aromatic ring in the C4 backbone leads to some preorganisation favouring cis chelation. It also shows a preference for low coordination numbers and this results in some unexpected products.

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More information

Published date: 6 January 2005
Keywords: diphosphine, metal complexes, x-ray structures, higher oxidation-states, bidentate phosphine-ligands, multi-dentatephosphorus, coordination chemistry, bi-dentate, rhodium(iii) complexes, crystal-structures, carbon sulfides, platinum(ii), palladium(ii)

Identifiers

Local EPrints ID: 20744
URI: https://eprints.soton.ac.uk/id/eprint/20744
ISSN: 0277-5387
PURE UUID: 468f5467-fd1d-41e3-a8ff-5139cce35ab3
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 02 Mar 2006
Last modified: 14 Jul 2018 00:37

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