Influence of the terminal ligands on the redox properties of the {Pt2(mu-S)2} core in [Pt2(Ph2X(CH2)2XPh2)2(mu-S)2] (X = P or As) complexes and on their reactivity towards metal centres, protic acids and organic electrophiles.
In order to explore possible ways for modulating the unusually rich chemistry shown by complexes of formula [L2Pt(mu-S)2PtL2] we have studied the influence of the nature of the terminal ligand L on the chemical properties of the {Pt2(mu-S)2} core. The systematic study we now report allows comparison of the behaviour of [Pt2(dpae)2(mu-S)2](dpae = Ph2As(CH2)2AsPh2) (1) with the already reported analogue [Pt2(dppe)2(mu-S)2](dppe = Ph2P(CH2)2PPh2). Complex 1 as well as the corresponding multimetallic derivatives [Pt(dpae){Pt2(dpae)2(mu-S)2}](BPh4)2 2, [M{Pt2(dpae)2(mu-S)2}2]X2 (M = Cu(II), X = BF4 3; M = Zn(II), X = BPh4 4; M = Cd(II), X = ClO4 5; M = Hg(II), X = Cl 6 or X2 = Cl(1.5)[HCl2](0.5) 6') have been characterized in the solid phase and in solution. Comparison of structural parameters of 1 and 3-6' with those of the corresponding phosphine analogues, together with the results of the electrochemical study for 1, allow us to conclude that replacement of dppe by dpae causes a decrease in basicity of the {Pt2(mu-S)2} core. The study of the reactivity of 1 towards CH2Cl2 and protic acids has led to the structural characterization of [Pt(dpae)(S2CH2)] 9 and [PtCl2(dpae)] 10. Moreover, comparison with the reactivity of [Pt2(dppe)2(mu-S)2] indicates that the stability of the intermediate species as well as the nature of the final products in both multistep reactions are sensitive to the nature of the terminal ligand.
Novio
Fernando
F
Departament de Química, Universitat Autònoma de Barcelona, E-08193, Bellaterra, Barcelona, Spain.
Mas-Ballesté
Rubén
R
Gallardo
Iluminada
I
González-Duarte
Pilar
P
Lledós
Agustí
A
Vila
Neus
N
D001151:Arsenic / Q000737:chemistry; D018360:Crystallography, X-Ray; D006851:Hydrochloric Acid / Q000737:chemistry*; D008024:Ligands; D019216:Metals, Heavy / Q000737:chemistry; D008752:Methylene Chloride / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009944:Organoplatinum Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010472:Perchlorates / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry; D013237:Stereoisomerism
D008024:Ligands; D019216:Metals, Heavy; D009944:Organoplatinum Compounds; D010472:Perchlorates; D010758:Phosphorus; D008752:Methylene Chloride; D001151:Arsenic; D006851:Hydrochloric Acid