The Relative Coordinating Ability of Some Weak O‐Donor Anions and Water Towards the [Pt(terpy)]²⁺ (terpy = 2,2′:6′,2″‐terpyridine) Center – X‐ray Crystal Structures of [Pt(terpy)(H₂O)](CF₃SO₃)₂ and [Pt₂(μ‐OH)(terpy)₂](PF₆)₂(CF₃SO₃)

Abstract

Abstract Acidolysis of the complexes [Pt(CH 3 )(terpy)]Y (Y = PF 6 , CH 3 SO 3 , CF 3 SO 3 , ClO 4 , BF 4 ; terpy = 2,2′:6′,2″‐terpyridine) with an equimolar amount of CH 3 SO 3 in 2,2,2‐trifluoroethanol (TFE) affords the corresponding methanesulfonato derivatives [Pt(OSO 2 CH 3 )(terpy)]Y. When Y = NO 3 a nearly equimolar mixture of the methanesulfonato and nitrato complexes is obtained, whereas the reaction of [Pt(CH 3 )(terpy)](CF 3 SO 3 ) with triflic acid in either dry TFE or CH 2 Cl 2 gives the aqua species [Pt(terpy)(H 2 O)](SO 3 CF 3 ) 2 ( 8′ ), whose X‐ray crystal structure is reported. This structure shows hydrogen bonding between the coordinated water molecule and two triflate ions. 1 H NMR evidence is reported that suggests that this hydrogen bonding is partially retained in CD 3 NO 2 solution. The new hydroxido‐bridged dimers [Pt 2 (μ‐OH)(terpy) 2 ](X) [X = (ClO 4 ) 3 , (PF 6 ) 2 (CF 3 SO 3 ) ( 12 )] have been isolated and their X‐ray crystal structures determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)