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An unexpected entry into the silver(I) chemistry of diphosphazane ligands: Crystal and molecular structures of $[Ag{Ph_2PN(Pr^i)PPh_2}(CF_3SO_3)]_2,$ $[Ag{Ph_2PN(Pr^i)PPh(OC_6H_3Me_2-2,6)}2]PF_6$, and $ [Ag_3(\mu-Cl)_2{Ph_2PN(R)PPh_2}3] PF_6 (R = H, Pr^i)$

Krishna, Heera and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam (2006) An unexpected entry into the silver(I) chemistry of diphosphazane ligands: Crystal and molecular structures of $[Ag{Ph_2PN(Pr^i)PPh_2}(CF_3SO_3)]_2,$ $[Ag{Ph_2PN(Pr^i)PPh(OC_6H_3Me_2-2,6)}2]PF_6$, and $ [Ag_3(\mu-Cl)_2{Ph_2PN(R)PPh_2}3] PF_6 (R = H, Pr^i)$. In: Polyhedron, 25 (16). pp. 3189-3200.

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Abstract

Mononuclear, binuclear and trinuclear silver(I) complexes were obtained unexpectedly while probing the reactivity of diphosphazane ligands of the type $X_2PN(Pr^i)PXY$ towards the ruthenium-based precursor $Ru(bipy)_2Cl_2 · 2H_2O$, in the presence of a silver salt as a chloride scavenger. Subsequently, the reactions of $AgX [X = Cl, NO_3 or CF_3SO_3]$ with $Ph_2PN(R)PPh(Y) [R = H, Y = Ph; R = Pr^i, Y = Ph or OC_6H_3Me_2-2, 6]$ in a 1:1 or 1:2 molar ratio have been investigated. Mononuclear or binuclear Ag(I) complexes containing either chelating or bridging diphosphazane ligands are obtained. Trinuclear silver(I) complexes are accessible by the treatment of diphosphazane ligands, $Ph_2PN(R)PPh_2 [R = H, Pr^i]$ with AgCl using piperidine as the solvent. In the presence of a suitable chloride donor species, the mononuclear and binuclear complexes of $Ph_2PN(Pr^i)PPh_2$ are transformed slowly to the trinuclear complex $[Ag_3(\mu-Cl)_2{Ph_2PN(Pr^i)PPh_2}_3]X$, over a period 20 h. The structures of representative complexes have been confirmed by X-ray crystallography and the salient structural features are discussed.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier.
Keywords: Phosphorus ligands;Silver(I) complexes;NMR spectroscopy;X-ray crystallography
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 16 May 2008
Last Modified: 19 Sep 2010 04:44
URI: http://eprints.iisc.ernet.in/id/eprint/13993

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